[ CAS No. 13755-29-8 ] {[proInfo.proName]}

Name: 13755-29-8|Sodium fluoroborate|99%
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Quality Control of [ 13755-29-8 ]

COA NMR CNMR HPLC LC-MS

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Product Details of [ 13755-29-8 ]

CAS No. :	13755-29-8	MDL No. :	MFCD00003515
Formula :	BF₄Na	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	KGJZTOFHXCFQIV-UHFFFAOYSA-N
M.W :	109.79	Pubchem ID :	4343483
Synonyms :

Safety of [ 13755-29-8 ]

Signal Word:	Danger	Class:	8
Precautionary Statements:	P501-P260-P270-P271-P264-P280-P314-P303+P361+P353-P301+P330+P331-P363-P304+P340+P310-P305+P351+P338+P310-P403+P233-P405	UN#:	1759
Hazard Statements:	H314-H372-H335	Packing Group:	Ⅱ
GHS Pictogram:

Application In Synthesis of [ 13755-29-8 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 13755-29-8 ]
Downstream synthetic route of [ 13755-29-8 ]

[ 13755-29-8 ] Synthesis Path-Upstream 1~7

1
[ 13755-29-8 ]
[ 104-94-9 ]
[ 459-64-3 ]

Reference： [1] Journal of Organic Chemistry, 2017, vol. 82, # 7, p. 3622 - 3630
[2] Tetrahedron Letters, 2017, vol. 58, # 19, p. 1834 - 1838

2
[ 13755-29-8 ]
[ 100-58-3 ]
[ 143-66-8 ]

Reference： [1] Bull. Acad. Sci. USSR, Div. Chem. Sci., 1955, p. 167[2] Izv. Akad. Nauk SSSr, Otd. Khim. Nauk, 1955, p. 187
[3] Zhurnal Analiticheskoi Khimii, 1959, vol. 14, p. 519 - 521[4] Zhurnal Analiticheskoi Khimii, 1959, vol. 14, p. 483 - 484
[5] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1955, p. 167[6] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1955, p. 187
[7] , Gmelin Handbook: Na: SVol.3, 4.3, page 1305 - 1312,
[8] , Gmelin Handbook: Na: SVol.3, 3.7, page 1233 - 1245,

3
[ 13755-29-8 ]
[ 100-58-3 ]
[ 7647-14-5 ]
[ 143-66-8 ]

Reference： [1] Zhurnal Obshchei Khimii, [2] Zhurnal Obshchei Khimii, 1962, vol. 32, p. 1358 - 1359
[3] , Gmelin Handbook: B: B-Verb.8, 11.2.4.1, page 173 - 175,
[4] Zhurnal Obshchei Khimii, [5] Zhurnal Obshchei Khimii, 1961, vol. 31, p. 2922 - 2923
[6] , Gmelin Handbook: B: B-Verb.8, 11.2.4.1, page 173 - 175,
[7] Bull. Acad. Sci. USSR Div. Chem. Sci., 1955, p. 167
[8] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, [9] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1955, p. 187
[10] , Gmelin Handbook: B: B-Verb.8, 11.2.4.1, page 173 - 175,

4
[ 13755-29-8 ]
[ 33462-80-5 ]
[ 33462-81-6 ]

Reference： [1] Patent: US4251521, 1981, A,

5
[ 13755-29-8 ]
[ 140681-55-6 ]

Reference： [1] Inorganic Chemistry, 2018, vol. 57, # 16, p. 10153 - 10159

6
[ 13755-29-8 ]
[ 328-70-1 ]
[ 79060-88-1 ]

Yield	Reaction Conditions	Operation in experiment
82%	With magnesium; ethylene dibromide In diethyl ether at 20℃; Inert atmosphere; Heating	A three-neck round bottom flask fitted with a reflux condenser was evacuated, flame dried and filledwith argon prior to use. 1.01 g (41.7 mmol) magnesium, 0.72 g (6.4 mmol, 1 eq) NaBF4 and diethylether (150 mL) were added. To start to reaction 1.07 g (0.49 ml, 5.7 mmol, 0.9 eq) dibromoethanewere added and the flask was heated for several minutes followed by the dropwise addition of 1.71 g(6.25 ml, 36 mmol) 3,5-bis(trifluoromethyl)bromobenzene diluted with diethyl ether (50 mL) over30 min. When the exothermic reaction slowed the reaction mixture was heated for additional 30 min.The solution was then stirred over night at room temperature. The reaction mixture was quenched bythe addition of 16 g Na2CO3 in distilled water (200 mL), stirred for 30 min and filtered. The aqueousphase was extracted three times with diethyl ether (50 mL), the combined organic phases were driedover sodium sulfate and charcoal followed by filtration. The solvent was removed and the remainingcrude product was dissolved in toluene (200 mL) to remove the water with a Dean Stark trap byazeotropic distillation. The solvent was removed, the product filtered, washed with dry toluene anddried under vacuo. The product was observed as colorless solid (4.65 g, 5.3 mmol, 82 percent).m.p. decomposition >290 °C.1H-NMR (300 MHz, DMSO-d6): δ = 7.67 (s, 4H, B-p-CH), 7.61 (s, 8H, B-o-CH) ppm.13C-NMR (75.5 MHz, DMSO-d6): δ = 161.0 (q, JB = 50 Hz, 4 Ci-B), 134.0 (s, 8 B-o-CH), 128.5 (qq,JF = 31 Hz, JB = 2.7 Hz, 8 Ci-CF3), 124.0 (q, JF = 272 Hz, CF3), 117.6 (m, 4 B-p-CH) ppm.19F-NMR (283 MHz, DMSO-d6): δ = -57.6 (CF3) ppm.Elemental analysis for C32H12BF24Na*1.8 H2O: calcd. C = 41.61 H = 1.70, found C = 41.57, H = 1.66.

Reference： [1] Inorganic Chemistry, 2014, vol. 54, # 1, p. 359 - 369
[2] Inorganic Chemistry, 2014, vol. 54, # 1, p. 359 - 369
[3] Tetrahedron Letters, 2016, vol. 57, # 31, p. 3453 - 3456
[4] Organic Syntheses, 2008, vol. 85, p. 248 - 266
[5] Journal of the American Chemical Society, 2001, vol. 123, # 44, p. 11020 - 11028
[6] Organometallics, 1992, vol. 11, p. 3920 - 3922
[7] Organometallics, 2005, vol. 24, # 14, p. 3579 - 3581
[8] Angewandte Chemie - International Edition, 2018, vol. 57, # 40, p. 13335 - 13338[9] Angew. Chem., 2018, vol. 130, p. 13519 - 13522,4

7
[ 13755-29-8 ]
[ 59237-50-2 ]
[ 166742-24-1 ]
[ 166742-16-1 ]

Reference： [1] Patent: EP741707, 1998, B1,

[ 13755-29-8 ] Synthesis Path-Downstream 1~109

1
[ 13755-29-8 ]
[ 171058-17-6 ]
[ 244193-50-8 ]

Reference： [1]Patent: US6339182,2002,B1 .Location in patent: Table 1
[2]Journal of the American Chemical Society,2017,vol. 139,p. 2176 - 2179

2
[ 13755-29-8 ]
[ 59237-50-2 ]
[ 166742-24-1 ]
[ 166742-16-1 ]

Yield	Reaction Conditions	Operation in experiment
	With concentrated hydrochloric acid; potassium carbonate; trifluoroacetic acid; sodium nitrite; In methyl 5-amino-6-(methylthio)nicotinate; water;	REFERENCE EXAMPLE 46 concentrated hydrochloric acid (9.06 ML) is added to a stirred suspension of methyl 5-amino-6-methoxynicotinate (3.3 g) in water (20 ML). The mixture is cooled to 0C and treated dropwise with a solution of sodium nitrite (1.37 g) in water (5 ML). After 30 minutes at 0C a solution of sodium tetrafluoroborate (2.84g) in water (10 ML) is added. After a further 30 minutes the precipitated diazonium salt is collected, washed with a little ice-cold water, and then with diethyl ether, and sucked dry. potassium carbonate (1.0g) is added to trifluoroacetic acid (32 ML) at 0C, followed by the addition of the diazonium salt, in one portion. The mixture is stirred at reflux for 18 hours, cooled, then poured into iced water and stirred for 1 hour. The aqueous mixture is neutralized by treatment with solid sodium bicarbonate and extracted with ethyl acetate. The extract is washed with water, dried over magnesium sulphate, and concentrated in vacuo, to give methyl 5-hydroxy-6-methoxynicotinate (2.86 g), in the form of a beige solid. This material is used without further purification. By proceeding in a similar manner using methyl 5-amino-6-(methylthio)nicotinate instead of methyl 5-amino-6-methoxynicotinate as the starting material, there is prepared methyl 5-hydroxy-6-(methylthio)nicotinate.

Reference： [1]Patent: EP741707,1998,B1

3
[ 13755-29-8 ]
[ 33462-80-5 ]
[ 33462-81-6 ]

Yield	Reaction Conditions	Operation in experiment
	With tetrafluoroboric acid; sodium; In tetrahydrofuran; dichloromethane; water;	EXAMPLE 2 Cyclopropyldiphenylsulfonium tetrafluoroborate STR18 A suspension of 3-chloropropyldiphenylsulfonium tetrafluoroborate (118.7 g, 0.339 mol) in dry tetrahydrofuran (500 ml) is placed in a 2 liter flask under nitrogen. Then 5 g. portions of a 55% sodium hydridemineral oil dispersion (15.2 g, 0.350 mol), are added in 0.5-hr. intervals. The resulting mixture is stirred at room temperature for 24 hr. A solution of 25 ml of 48% tetrafluoroboric acid, 15 g of sodium tetrafluoroborate, and 400 ml of water are added to destroy residual hydride and swamp out chloride ion. After 5 min., methylene chloride (300 ml) is added, and the methylene chloride layer is removed from the lower aqueous layer. As the densities of the methylene chloride and water layers are nearly equal, caution is required in recovering the desired methylene chloride layer; the aqueous layer is retained for further extraction. The methylene chloride solution is then washed with 100 ml of water; the aqueous layer is separated and combined with the first aqueous layer. The combined water layers are extracted with an additional 100 ml of methylene chloride. The methylene chloride portions are combined, dried over anhydrous sodium sulfate, and evaporated in vacuo until precipitation occurs. The title product is precipitated upon addition of ether (1 liter). The solid product is collected, washed with ether, and recrystallized from absolute ethanol (approximately 400 ml) and dried in vacuo, mp 139. Repeating the procedure of this example, but using in place of the 3-chloropropyldiphenylsulfonium tetrafluoroborate, an equivalent amount of:

Reference： [1]Patent: US4251521,1981,A

4
[ 13755-29-8 ]
[ 24279-39-8 ]
[ 77227-81-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium nitrite; In hydrogenchloride; water;	(a) Preparation of 3,5-dichloro-4-fluorobenzotrifluoride 2,6-Dichloro-4-trifluoromethylaniline (6.5 g) in concentrated hydrochloric acid (18 ml) was cooled to 0 C. Sodium nitrite (1.95 g) dissolved in a little water was added slowly while the solution was stirred and kept below 5 C. When addition was complete the solution was stirred for 1 hour, filtered, and added to a solution of sodium fluoroborate (6 g) in water (10 ml). The precipitate was washed with a little cold water and with ether, and dried. The solid was heated with the flame of a Bunsen burner until decomposition took place; the product distilled from the reaction flask and was collected, taken up in ether, and washed with water. The ether solution was dried and evaporated to give an oil, which was distilled under reduced pressure to give the benzotrifluoride derivative (1.5 g).

Reference： [1]Patent: US4388472,1983,A

5
sodium hexaflorophosphate [ No CAS ]
lithium tetrafluoroborate [ No CAS ]
[ 13755-29-8 ]
[ 21324-40-3 ]

Reference： [1]Zeitschrift fur Anorganische und Allgemeine Chemie,2005,vol. 631,p. 1840 - 1842

6
[ 13755-29-8 ]
[ 93127-75-4 ]
bis(2,2'-bipyridine)dichlororuthenium(II) dihydrate [ No CAS ]
{Ru(dabp)(bpy)2}(BF₄)2 [ No CAS ]

Reference： [1]Bulletin of the Chemical Society of Japan,1990,vol. 63,p. 1299 - 1304

7
[ 13755-29-8 ]
[ 52462-29-0 ]
[ 27069-17-6 ]
{(η6-p-cymene)RuCl(3-(4'-methoxyphenyl)pyrazole)2}BF4 [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1994,vol. 124,p. 35 - 42

8
[ 13755-29-8 ]
[ 52462-29-0 ]
[ 59843-75-3 ]
{(η6-p-cymene)RuCl(3-(4'-methylphenyl)pyrazole)2}BF4 [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1994,vol. 124,p. 35 - 42

9
[ 13755-29-8 ]
[ 52462-29-0 ]
[ 59843-58-2 ]
{(η6-p-cymene)RuCl(3-(4'-chlorophenyl)pyrazole)2}BF4 [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1994,vol. 124,p. 35 - 42

10
[ 13755-29-8 ]
{Pd(6-methyl-2,2'-bipyridine)Cl₂} [ No CAS ]
[ 56100-22-2 ]
{Pd((C₅H₄N)(C₅H₃N(CH₃)))2Cl}⁽¹⁺⁾*BF₄^(1-)={Pd((C₅H₄N)(C₅H₃N(CH₃)))2Cl}BF₄ [ No CAS ]

Reference： [1]Australian Journal of Chemistry,1991,vol. 44,p. 219 - 232

11
[ 13755-29-8 ]
[ 19978-61-1 ]
[ 74457-38-8 ]
[ 88083-20-9 ]

Reference： [1]Journal of the American Chemical Society,1983,vol. 105,p. 7767 - 7768

12
[ 13755-29-8 ]
copper(II) choride dihydrate [ No CAS ]
[ 4733-39-5 ]
bis(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)copper(II) tetrafluoroborate [ No CAS ]

Reference： [1]Inorganica Chimica Acta,1998,vol. 277,p. 31 - 36

13
[ 13755-29-8 ]
[ 19392-93-9 ]
[ 110-67-8 ]
[ 252659-29-3 ]

Reference： [1]Journal of Organometallic Chemistry,1999,vol. 589,p. 138 - 149

14
[ 13755-29-8 ]
[ 72905-30-7 ]
[ 131457-46-0 ]
lithium chloride [ No CAS ]
[Ru(2,2'-bis[2-[4(S)-phenyl-1,3-oxazolinyl]]propane)Cl(2,2':6',2''-terpyridine)]BF₄ [ No CAS ]

Reference： [1]Inorganic Chemistry,1995,vol. 34,p. 4198 - 4205
Inorg. Chem.,

15
[ 13755-29-8 ]
[ 79917-90-1 ]
[ 174501-65-6 ]

Yield	Reaction Conditions	Operation in experiment
86.7%	In acetone; at 20℃; for 48h;	The intermediate [Bmim] Cl50g withSodium borofluoride(According to the ratio of its mass is 1: 1.05)Join a three-necked flask with a stirring device,100mL acetone as the reaction medium,Mechanical stirring at room temperature 48h, suction filtration (acetone washing) to remove NaCl,Rotate to acetone, and then add CH2C12 wash,Swirl to remove CH2C12,The resulting ionic liquid was dried in a vacuum oven at 80 24hAfter the pale yellow transparent liquid 56.3g:which isl-Butyl-3-methylimidazolium tetrafluoroborateIonic Liquid ([Bmim]BF4) in a yield of 86.7%.
85.1%	In acetone; at 20℃; for 48h;	The intermediate product [Bmim] Cl 87g was mixed with sodium fluoroborate (1: 1.05 in terms of its mass ratio)Was added to a three-necked flask equipped with a stirrer,To l0mL acetone as the reaction medium, room temperature mechanical stirring 48h,Pumping (acetone wash) to remove NaCl,Steamed to acetone, then add CH2C12 washing,The CH2C12 was removed by steaming and the resulting ionic liquid was dried in a vacuum oven at 80 C for 24 hAfter the light yellow transparent liquid 96.2g:Namely 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid([Bmim] BF4) in a yield of 85.1%.
85.4%	In acetone; at 20℃; for 48h;	The intermediate [Bmim] Cl 50g and sodium borofluoride (according to the ratio of its mass of 1: 1.05) was added to a three-necked flask equipped with a stirring device,100mL acetone as the reaction medium,Mechanical stirring at room temperature 48h,Suction filtration (acetone wash) to remove NaCl,Rotate to acetone,Then add CH2C12 washing,Swirl to remove CH2C12,The resulting ionic liquid was dried in a vacuum oven at 80 C for 24 hours to obtain 55.5g of light yellow transparent liquid: l-butyl-3-methylimidazolium tetrafluoroborate ionic liquid ([Bmim] BF4)Yield 85.4%.

80%	In water; at 25 - 80℃; under 0.000750075 Torr; for 10.5h;	(1) at room temperature about 25 o C lower, will 103g sodium four fluorine boron (NaBF 4) is added to 100 ml of deionized water, 500 ml flask, mechanical stirring 30 minutes, so as to form saturated NaBF 4 aqueous solution, with a small amount of solid remaining at the bottom of the; (2) in the above-mentioned saturated solution continue adding 0.5mol/55gNaBF 4 and 0.5mol/87 g1-butyl-3-methyl imidazole chlorine salt BMImCl; (3) mechanical stirring 30 minutes, the full reaction; (4) standstill after the reaction, the solution is divided into three layers: the upper layer is mainly ionic liquid BMImBF 4, the middle layer is a saturated aqueous solution, the bottom layer is mainly solid inorganic salt NaCl by-product, is transferred to the solution in the separatory funnel, the remaining bottom layer for NaCl solid non-polar by-products. (5) solution of layering in the separatory funnel, the upper layer of the ionic liquid solution, the lower is the saturated aqueous solution, with the liquid, in the ionic liquid remain in the separatory funnel, for collecting the lower saturated aqueous solution. (6) to the above-mentioned is the ionic liquid solution to add a new configuration of the separatory funnel in NaBF 4 saturated aqueous solution 20 ml, fully after shaking, static hierarchical. Separating processing, the ionic liquid solution in the separatory funnel, for collecting liquid, so repeat two; (7) of the above-mentioned ionic liquid solution after washing transferred to the 250 ml round-bottom flask in grinding port, the magnetic stirring, 80 o C and 0.1 Pa vacuum drying under the conditions of 10 hours, filtering after standing, shall be 90g nocolor ionic liquid BMImBF 4, the yield is 80%. (8) in the above-mentioned step (4) the resulting solid inorganic salt by-product filter NaCl, new configuration for NaCl saturated aqueous solution of washing 3 times, each time the amount of 50 ml; (9) the above-mentioned inorganic salt NaCl transfer to 50 ml beaker, in 80 o C and 0.1 Pa dried in vacuum oven for 10 hours, to obtain 20g white solid NaCl, for the recovery of by-products 70%; (10) of step (5) collection of the lower saturated aqueous solution and step (6) of the collected liquid to be mixed to be mixed, mixed solution is mainly containing anion precursor saturated aqueous solution of inorganic salts, can be used repeatedly, that is, repeating the above-mentioned step (2), (3), (4), (5), (6), (7), (8), (9).
	In water; for 24h;	Preparation of 1-butyl-3-methylimidazolium tetrafluoroborate; Methylimidazole and excessive amount of chloro-n-butane (molar ratio: 1/1.05) were reacted at 70 C. with stirring for 48 hours. Excessive of reactants were removed by rotary evaporation, thereby 1-butyl-3-methylimidazolium chloride was obtained. The obtained 1-butyl-3-methylimidazolium chloride was further added into an aqueous solution with excessive amount of sodium tetrafluoroborate (molar ratio: 1/1.1) and stirred for 24 hours. Then, adequate amount of methylene dichloride was added to extract the product. A mixture of the product and the methylene dichloride was washed with water until no chlorine ion was detected by a silver nitrate solution (0.1 mol/L). A product of 1-butyl-3-methylimidazolium tetrafluoroborate was obtained after removing methylene dichloride in the product by rotary evaporation and drying.

Reference： [1]Green Chemistry,2017,vol. 19,p. 1303 - 1307
[2]Journal of the Electrochemical Society,2003,vol. 150,p. E307-E311
[3]Organic Syntheses,2005,vol. 82,p. 166 - 169
[4]Organic and Biomolecular Chemistry,2018,vol. 16,p. 3453 - 3463
[5]Patent: CN106632051,2017,A .Location in patent: Paragraph 0025; 0027; 0028
[6]Patent: CN106632052,2017,A .Location in patent: Paragraph 0027; 0029
[7]Patent: CN106588778,2017,A .Location in patent: Paragraph 0033; 0035; 0036
[8]Patent: CN105481773,2016,A .Location in patent: Paragraph 0023
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[10]Organic and Biomolecular Chemistry,2019,vol. 17,p. 9336 - 9342
[11]RSC Advances,2016,vol. 6,p. 90273 - 90279
[12]Patent: US2011/21846,2011,A1 .Location in patent: Page/Page column 3
[13]Journal of Physical Chemistry B,2004,vol. 108,p. 16593 - 16600
[14]RSC Advances,2013,vol. 3,p. 13825 - 13834
[15]Asian Journal of Chemistry,2014,vol. 26,p. 2695 - 2698
[16]Inorganic Chemistry,2019,vol. 58,p. 1764 - 1773

16
[ 13755-29-8 ]
[ 1003-56-1 ]
[ 364617-97-0 ]
silver nitrate [ No CAS ]
bis(μ-3-methyl-2-pyridone)bis[((2,2'-dipyridyl)propylamine)platinum(II)]tetrafluoroborate [ No CAS ]

Reference： [1]Inorganica Chimica Acta,2001,vol. 319,p. 109 - 116

17
[ 254-60-4 ]
[ 366-18-7 ]
[ 13755-29-8 ]
ruthenium(III) chloride trihydrate [ No CAS ]
[Ru(2,2'-bipyridyl)(1,8-naphthyridine)2Cl]BF₄ [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,1999,vol. 38,p. 362 - 363

18
[ 13755-29-8 ]
dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer [ No CAS ]
[ 148461-14-7 ]
[(η5-C5Ne5)RhCl((4S)-2-(2-diphenylphosphino)phenyl)-4-isopropyl-1,3-oxazoline)](BF4) [ No CAS ]

Reference： [1]Organometallics,2002,vol. 21,p. 5100 - 5114

19
[ 13755-29-8 ]
[ 12354-84-6 ]
[ 148461-14-7 ]
[(η5-C5Ne5)IrCl((4S)-2-(2-diphenylphosphino)phenyl)-4-isopropyl-1,3-oxazoline)](BF4) [ No CAS ]

Reference： [1]Organometallics,2002,vol. 21,p. 5100 - 5114

20
[ 13755-29-8 ]
bis(η3-allyl-μ-chloropalladium(II)) [ No CAS ]
[ 13406-29-6 ]
[ 658062-42-1 ]

Reference： [1]Journal of Organometallic Chemistry,2003,vol. 687,p. 365 - 376

21
[ 14264-16-5 ]
[ 13755-29-8 ]
[ 13040-77-2 ]
nickel hexammine tetrafluoroborate [ No CAS ]
Ni(H₂O)2(C₂₀H₁₄N₄)⁽²⁺⁾*2BF₄^(1-) = [Ni(H₂O)2(C₂₀H₁₄N₄)](BF₄)2 [ No CAS ]

Reference： [1]Journal of the Chemical Society, Dalton Transactions,1996,p. 2423 - 2433

22
[ 13755-29-8 ]
[ 61250-65-5 ]
[ 1179-06-2 ]
Pt₂(((C₆H₅)2P)2CH₂)2(((C₆H₅)2P)2C₆H₄)⁽²⁺⁾*2BF₄^(1-)=[Pt₂(((C₆H₅)2P)2CH₂)2(((C₆H₅)2P)2C₆H₄)](BF₄)2 [ No CAS ]

Reference： [1]Organometallics,1996,vol. 15,p. 5321 - 5329

23
[ 13755-29-8 ]
chlorobis(cyclooctene)-iridium(I) dimer [ No CAS ]
[ 148461-14-7 ]
iridium(III)bis[(4S)-2-[2-(diphenylphosphanyl)phenyl]-4-isopropyl-1,3-oxazoline] tetrafluoroborate [ No CAS ]

Reference： [1]European Journal of Inorganic Chemistry,2005,p. 1657 - 1664

24
[ 13755-29-8 ]
[ 19978-61-1 ]
[ 4403-71-8 ]
[ 635-93-8 ]
[ 868961-96-0 ]

Reference： [1]Organometallics,2005,vol. 24,p. 5479 - 5483

25
[ 13755-29-8 ]
[ 52462-29-0 ]
[ 148461-14-7 ]
[(η6-p-MeC6H4(i)Pr)RuCl((4S)-2-(2-diphenylphosphinophenyl)-4-isopropyl-1,3-oxazoline)][BF4] [ No CAS ]

Reference： [1]Organometallics,2006,vol. 25,p. 1592 - 1606

26
[ 13755-29-8 ]
[ 352232-62-3 ]
[ 15492-38-3 ]
Rh[Ni(CH₂)9N₂S₂]3⁽³⁺⁾*3BF₄^(1-)=Rh[Ni(CH₂)9N₂S₂]3(BF₄)3 [ No CAS ]

Reference： [1]Dalton Transactions,2006,p. 4244 - 4252

27
[ 13755-29-8 ]
[ 19978-61-1 ]
[ 90-02-8 ]
[ 100-46-9 ]
[ 868962-04-3 ]

Reference： [1]Organometallics,2005,vol. 24,p. 5479 - 5483

28
[ 254-60-4 ]
dirhodium tetraacetate [ No CAS ]
[ 13755-29-8 ]
[ 92404-56-3 ]
cis-[Rh2(μ-O2CCH3)2(1,8-naphthyridine)(2-(2-pyridyl)-1,8-naphthyridine)](BF4)2 [ No CAS ]

Reference： [1]Inorganic Chemistry,2007,vol. 46,p. 7494 - 7502

29
[ 13755-29-8 ]
[ 100125-12-0 ]
cis-dichlorobis(2,2'-bipyridine)ruthenium(II) hydrate [ No CAS ]
bis(2,2'-bipyridine)(3,8-dibromo-1,10-phenanthroline)ruthenium(II) tetrafluoroborate - trihydrate [ No CAS ]

Reference： [1]European Journal of Inorganic Chemistry,2009,p. 1321 - 1330

30
[ 13755-29-8 ]
[ 66127-01-3 ]
[ 64-17-5 ]
cis-dichlorobis(2,2'-bipyridine)ruthenium(II) hydrate [ No CAS ]
bis(2,2'-bipyridine)(3-bromo-1,10-phenanthroline)ruthenium(II) tetrafluoroborate - ethanol - water (1/1/2) [ No CAS ]

Reference： [1]European Journal of Inorganic Chemistry,2009,p. 1321 - 1330

31
[ 13755-29-8 ]
copper(II) choride dihydrate [ No CAS ]
[ 3847-57-2 ]
[ 1175003-80-1 ]
[Cu₂(N,N,N',N'-tetrakis(N-propyl-2-benzimidazolyl)-2-hydroxy-1,3-diaminopropane^(1-))(nitrobenzoate)](BF₄)2*H₂O [ No CAS ]

Reference： [1]Inorganic Chemistry,2009,vol. 48,p. 7244 - 7250

32
[ 13755-29-8 ]
[ 35935-34-3 ]
[ 143314-16-3 ]

Reference： [1]Chemical Physics Letters,2008,vol. 461,p. 229 - 234

33
[ 13755-29-8 ]
[RuCl₂(hexamethylbenzene)]2 [ No CAS ]
[ 72-80-0 ]
[ 1202404-57-6 ]

Reference： [1]Journal of Organometallic Chemistry,2009,vol. 694,p. 3973 - 3981

34
[ 13755-29-8 ]
[ 72-80-0 ]
[ 52462-29-0 ]
[ 1202404-49-6 ]

Reference： [1]Journal of Organometallic Chemistry,2009,vol. 694,p. 3973 - 3981

35
[ 616-47-7 ]
[ 13755-29-8 ]
[ 2366-52-1 ]
[ 174501-65-6 ]

Reference： [1]Journal of Physical Chemistry B,2010,vol. 114,p. 9201 - 9208

36
[ 13755-29-8 ]
[ 2304-30-5 ]
tetra-n-butylphosphonium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In water; for 24h;	Preparation of Tetrabutylphosphonium Tetrafluoroborate:; Tetrabutylphosphonium chloride was added into an aqueous solution with excessive amount of sodium tetrafluoroborate (molar ratio: 1/1.1) and stirred for 24 hours. Then, adequate amount of methylene dichloride was added to extract the product. A mixture of the product and the methylene dichloride was washed with water until no chlorine ion was detected by a silver nitrate solution (0.1 mol/L). A product of tetrabutylphosphonium tetrafluoroborate was obtained after removing methylene dichloride in the product by rotary evaporation and drying.

Reference： [1]Patent: US2011/21846,2011,A1 .Location in patent: Page/Page column 3

37
[ 13755-29-8 ]
[ 66-71-7 ]
[ 16490-02-1 ]
manganese(II) chloride dihydrate [ No CAS ]
[ 7732-18-5 ]
Mn4(μ-pyrimidine-4,6-dicarboxylate)3(H2O)4(1,10-phenanthroline)(BF4)2*11H2O [ No CAS ]

Reference： [1]European Journal of Inorganic Chemistry,2011,p. 68 - 77

38
[ 67-56-1 ]
[ 13755-29-8 ]
[ 111975-10-1 ]
[ 60-29-7 ]
[ 131833-89-1 ]
monochloro(N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4,5-dihydrooxazole-2-carbimidate)(trispyrazolylmethane)ruthenium(II)*2.5(methanol) [ No CAS ]
monochloro((4S,4'S)-(-)-4,4',5,5'-tetrahydro-4,4'-bis(1-methylethyl)-2,2'-bioxazole)(trispyrazolylmethane)ruthenium(II) tetrafluoroborate*1.7(diethyl ether) [ No CAS ]

Reference： [1]Inorganic Chemistry,2011,vol. 50,p. 6044 - 6054

39
[ 109-99-9 ]
[ 13755-29-8 ]
[ 26305-75-9 ]
[ 1282-37-7 ]
[ 151483-96-4 ]
[Co(1,3-diethyl-4,5-dimethylimidazole-2-ylidene)4]2[BF₄]*THF [ No CAS ]

Reference： [1]Organometallics,2011,vol. 30,p. 4687 - 4694

40
[ 13755-29-8 ]
[ 35047-29-1 ]
palladium dichloride [ No CAS ]
bis(di-(2-pyridyl)hydroxymethane)palladium(II) tetrafluoroborate [ No CAS ]

Reference： [1]Polyhedron,2012,vol. 36,p. 104 - 111

41
[ 13755-29-8 ]
[ 14871-92-2 ]
[ 25005-96-3 ]
[Pt(2,3-bis(pyridine-2-yl)-pyrazine)(en)](BF₄)2*H₂O [ No CAS ]

Reference： [1]Zeitschrift fur Anorganische und Allgemeine Chemie,2012,vol. 638,p. 1691 - 1698,8

42
[ 13755-29-8 ]
copper(II) nitrate trihydrate [ No CAS ]
[ 605-70-9 ]
[ 878132-19-5 ]
[(1-ethyl-3-methylimidazolium)NaCu(1,4-naphthalenedicarboxylate)₂]_n [ No CAS ]

Reference： [1]Inorganic Chemistry,2013,vol. 52,p. 6773 - 6775

43
[ 13755-29-8 ]
[ 999-81-5 ]
2-chloroethyltrimethylammonium tetrafluoroborate [ No CAS ]

Reference： [1]Central European Journal of Chemistry,2013,vol. 11,p. 1816 - 1821

44
[ 13755-29-8 ]
[ 100125-12-0 ]
[Na(3,8-dibromo-phen)BF₄]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.1%	In ethanol; water; for 2h;Reflux;	General procedure: A mixture of stoichiometric amounts of sodium tetrafluoroborate (0.110 g, 1.0 mmol) in 10 cm3 water and 3-bromo-phen (0.259 g, 1.0 mmol) in 40 cm3 ethanol was refluxed for 2 h. The mixture was cooled to room temperature and concentrated to nearly dry using a rotatory evaporator, and then the resulting precipitate 2 was filtered and washed by diethyl ether and dried in a vacuum. Yield: 0.28 g (75.9%).

Reference： [1]Inorganica Chimica Acta,2013,vol. 405,p. 1 - 8

45
[ 13755-29-8 ]
[ 66127-01-3 ]
[Na(3-bromo-phen)₂BF₄] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70.1%	In ethanol; water; at 20℃; for 2h;	A mixture of sodium tetrafluoroborate (0.055 g, 0.5 mmol) in 10 cm3 water and 3-bromo-phen (0.259 g, 1.0 mmol) in 40 cm3 ethanol was stirred at room temperature for 2 h. The mixture was concentrated to nearly dry using a rotatory evaporator, and then the resulting precipitate 1 was filtered and washed by diethyl ether and dried in a vacuum. Yield: 0.22 g (70.1%).

Reference： [1]Inorganica Chimica Acta,2013,vol. 405,p. 1 - 8

46
[ 13755-29-8 ]
[ 66127-01-3 ]
[Na(3-bromophen)BF₄]₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75.9%	In ethanol; water; for 2h;Reflux;	General procedure: A mixture of stoichiometric amounts of sodium tetrafluoroborate (0.110 g, 1.0 mmol) in 10 cm3 water and 3-bromo-phen (0.259 g, 1.0 mmol) in 40 cm3 ethanol was refluxed for 2 h. The mixture was cooled to room temperature and concentrated to nearly dry using a rotatory evaporator, and then the resulting precipitate 2 was filtered and washed by diethyl ether and dried in a vacuum. Yield: 0.28 g (75.9%).

Reference： [1]Inorganica Chimica Acta,2013,vol. 405,p. 1 - 8

47
[ 13755-29-8 ]
[ 847616-85-7 ]
[ 564483-18-7 ]
C₄₅H₅₉NPPd⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		A test tube, equipped with a magnetic stir bar and fitted with a Teflon screw-cap, was charged with mu-Cl dimer (78 mg, 0.125 mmol, 0.50 eq) and NaBF4 (165 mg, 1.50 mmol, 3.00 eq). The tube was sealed and evacuated and backfilled with argon (this was repeated two times), after which acetonitrile (3 mL) and methanol (1 mL) was added. After stirring for 30 min, <strong>[564483-18-7]XPhos</strong> (238 mg, 0.50 mmol, 1.00 eq) was added and rinsed down the sides of the tube with additional acetonitrile and the mixture was stirred overnight. After completion, the reaction mixture was eluted through celite and the solvent was removed via rotary evaporation. The residue was then triturated with pentane. The resulting solid was isolated via filtration and further dried under vacuum. See FIG. 20.

Reference： [1]Patent: US2013/331566,2013,A1 .Location in patent: Paragraph 0061; 0303

48
[ 13755-29-8 ]
[ 41748-71-4 ]
1H-indazole-4-diazonium tetrafluoroborate salt [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Step 3 To compound [67] (6.0 g, 0.045 mol) was added 6 M HC1 (70 ml) at -5 C followed by drop wise addition of an aqueous solution of sodium nitrite (3.42 g, 0.049 mol, in 1 1 ml water). The reaction mixture was stirred at -5 C for 30 min followed by addition of sodium tetrafluoroborate (7.4 g, 0.0675 mol). The reaction mixture was stirred for another 10 min ESIMS: 163 (M+ + 1)

Reference： [1]Patent: WO2014/16849,2014,A2 .Location in patent: Page/Page column 112; 113

49
[ 13755-29-8 ]
[ 874-80-6 ]
N-butylpyridinium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99.43%	In acetone; at 20℃; for 24h;	In another dry three-necked flask was added O. 2mo 1 N-butylpyridine bromide and 0.25mo 1 sodium borofluoride and 50ml acetone was warmed to 40 C, the reaction was stirred for 24 hours at the temperature was stirred, the reaction was monitored by suction filtration, The filtrate was concentrated under reduced pressure to give crude N-butylpyridinium tetrafluoroborate, the crude was dissolved in dichloromethane, filteredThe filtrate was concentrated under reduced pressure to give 44.2 g of N-butylpyridinium tetrafluoroborate as a light yellow liquid, yield 94.3%.
95.2%	In acetone; at 40℃; for 24h;	0.1 mol N-butylpyridinium bromide will be addedAnd 0.11 sodium fluoborate and 30 ml of acetone was added to a three-necked flask,Warmed to 40 C,The reaction was stirred for 24 hours,Monitoring reaction is completed,Suction filtration,The filtrate was concentrated under reduced pressure to give crude N-butylpyridinium tetrafluoroborate,Crude was dissolved in dichloromethane,filter,The filtrate was concentrated under reduced pressure to give 22.3 g of N-butylpyridinium tetrafluoroborate as a pale yellow liquid,Yield 95.2%.

Reference： [1]Patent: CN106632483,2017,A .Location in patent: Paragraph 0023
[2]Patent: CN106588779,2017,A .Location in patent: Paragraph 0024; 0026; 0027
[3]Russian Journal of General Chemistry,2013,vol. 83,p. 2062 - 2065
Zh. Obshch. Khim.,2013,vol. 83,p. 1868 - 1872,5

50
[ 13755-29-8 ]
[ 85100-78-3 ]
[ 244193-50-8 ]

Yield	Reaction Conditions	Operation in experiment
	In methanol; at 20℃; for 24h;	General procedure: Another anion exchange reaction was carried out to achieve IL with boron tetrafluorides as a counter anion (IL-BF4) by metathesis reaction as per reported literature with minor modifications (Scheme 2). A demonstrative example for the synthesis of [RMIM]BF4 (i.e., [EMIM]BF4, [BMIM]BF4, [HMIM]BF4, [OMIM]BF4, [DMIM]BF4) and [RBZMIM]BF4 (i.e., [EBZMIM]BF4, [BBZMIM]BF4, [HBZMIM]BF4, [OBZMIM]BF4, [DBZMIM]BF4) in Scheme 2 (step-3) derivatives are as follows: 1:2 ratio of the 1-methyl-3-alkylimidazolium bromide or 1-methyl-3-alkylbenzimidazolium bromide ([RBZMIM]Br) and NaBF4 were added distinctly in to the round bottom flask containing 25mL of methanol and stirred at room temperature for 24h. Afterward, the salt was removed by filtering the reaction mixture using Whatman filter paper. Further, the filtrate was centrifuged for 10min at 3000rpm to isolate the residual salts. Solvent was evaporated under reduced pressure, vacuum dried and characterized (using 1H and 13C NMR and mass spectroscopy). The spectral details of the synthesized ILs are provided in the supplementary information Figs. S1 to S30.

Reference： [1]Journal of Chemical and Engineering Data,2014,vol. 59,p. 540 - 553
[2]Journal of Molecular Liquids,2018,vol. 268,p. 156 - 168

51
[ 13755-29-8 ]
[ 33035-41-5 ]
[ 101251-09-6 ]
(mesityl)(4-acetamidophenyl)iodonium tetrafluoroborate [ No CAS ]

Reference： [1]Organic Letters,2014,vol. 16,p. 3224 - 3227

52
[ 13755-29-8 ]
[ 4761-00-6 ]
1-(imidazol-1-yl)-2-(dimethylaminomethyl)ferrocene [ No CAS ]
C₃₅H₄₃FeN₃⁽²⁺⁾*2BF₄^(1-) [ No CAS ]

Reference： [1]European Journal of Inorganic Chemistry,2015,vol. 2015,p. 609 - 616

53
ruthenium trichloride [ No CAS ]
[ 13755-29-8 ]
[ 66-71-7 ]
[ 33893-89-9 ]
[ 215611-93-1 ]
[Ru(6,7-dicyanodipyrido[2,2-d:2',3'-f]quinoxaline)(2-(1H-tetrazole-5-yl)pyridine)(1,10-phenanthroline)]BF₄ [ No CAS ]

Reference： [1]New Journal of Chemistry,2015,vol. 39,p. 3035 - 3042

54
[ 366-18-7 ]
[ 13755-29-8 ]
[ 33893-89-9 ]
rhodium(III) chloride hydrate [ No CAS ]
[ 215611-93-1 ]
[Ru(6,7-dicyanodipyrido[2,2-d:2',3'-f]quinoxaline)(2-(1H-tetrazole-5-yl)pyridine)(2,2-bipyridine)]BF₄ [ No CAS ]

Reference： [1]New Journal of Chemistry,2015,vol. 39,p. 3035 - 3042

55
[ 13755-29-8 ]
[ 85100-77-2 ]
[ 174501-65-6 ]

Yield	Reaction Conditions	Operation in experiment
95%Spectr.	In methanol; at 50℃; for 0.333333h;Microwave irradiation;	Synthesis of 1-Butyl-3-methylimidazolium tetrafluoroborate ([Bmim] BF4) in a two-step process Step 1: Synthesis of 1-butyl-3-methylimidazolium bromide salt ([Bmim] Br)To a 2000 ml round bottom flask was added 2.1 mol of bromo-n-butane, Further, 2 mol of N-methylimidazole was added to the constant-pressure dropping funnel, and the reaction was carried out in an ultrasonic-microwave combination reactor, The knob of the constant-pressure dropping funnel was controlled so that 2 mol of N-methylimidazole was dropped in two minutes, Set the ultrasonic power of 1200W, Microwave heating power of 1500W, The reaction was carried out at 100 C for 20 minutes. The content of [Bmim] Br in the reaction mixture was 98% by NMR and LC-MS. The second step: Synthesis of the target product [Bmim] BF4 To the above synthesized [Bmim] Br, 2 mol of sodium fluoroborate was added, Then add 500ml of methanol as solvent, In the 1000W ultrasound, 1200W microwave, 50 deg C for 20 minutes.The content of [Bmim] BF4 in the reaction mixture was determined to be up to 95% by nuclear magnetic resonance and liquid chromatography-mass spectrometry.
	In acetone; at 20℃;	In a round bottomflask, a mixture of 1-methyl imidazole (4 g; 48.78 mmol)and n-butyl bromide (6.7 g; 48.78 mmol) was stirred at 80 Cin neat condition for 10 h. After that, neutral ionic liquid[BMIM][Br] was obtained as white solid. The reaction mixturewas washed with ethyl acetate four times for completeremoval of n-butyl bromide and other organic compounds.It was then subjected to vacuum to obtain the pure solid[BMIM][Br]. After that, sodium tetrafluoroborate (5 g, 45.66mmol) was added to the [BMIM][Br] in acetone and stirredovernight at room temperature to obtain [BMIM][BF4]. Thesolution was filtered and and acetone was removed in vacuumto obtain the pure [BMIM][BF4] as colorless liquid.
	In dichloromethane; water; at 20℃; for 24h;	The obtained 1-methyl-3-butylimidazolium bromide was dissolved in methylene chloride, and an aqueous solution having a NaBF4 with content of 1 mol was added thereto, and the reaction was stirred at room temperature for 24 hours. After completion of the reaction, the methylene chloride phase was washed with a small amount of water for several times, and then the methylene chloride was removed by a rotary evaporator and vacuum dried to give an ionic liquid 1-methyl-3-butylimidazolium tetrafluoroborate

	In dichloromethane; water; at 20℃; for 24h;	The obtained 1-methyl-3-butylimidazolium bromide was dissolved in methylene chloride, an aqueous solution having a NaBF4 content of 1 mol was added to the solution, and the reaction was stirred at room temperature for 24 hours. After completion of the reaction, the methylene chloride phase was washed with a small amount of water to remove ions, and methylene chloride was removed and dried in vacuo to obtain 1-methyl-3-butylimidazolium tetrafluoroborate salt as an ionic liquid.
	In methanol; at 20℃; for 24h;	General procedure: Another anion exchange reaction was carried out to achieve IL with boron tetrafluorides as a counter anion (IL-BF4) by metathesis reaction as per reported literature with minor modifications (Scheme 2). A demonstrative example for the synthesis of [RMIM]BF4 (i.e., [EMIM]BF4, [BMIM]BF4, [HMIM]BF4, [OMIM]BF4, [DMIM]BF4) and [RBZMIM]BF4 (i.e., [EBZMIM]BF4, [BBZMIM]BF4, [HBZMIM]BF4, [OBZMIM]BF4, [DBZMIM]BF4) in Scheme 2 (step-3) derivatives are as follows: 1:2 ratio of the 1-methyl-3-alkylimidazolium bromide or 1-methyl-3-alkylbenzimidazolium bromide ([RBZMIM]Br) and NaBF4 were added distinctly in to the round bottom flask containing 25mL of methanol and stirred at room temperature for 24h. Afterward, the salt was removed by filtering the reaction mixture using Whatman filter paper. Further, the filtrate was centrifuged for 10min at 3000rpm to isolate the residual salts. Solvent was evaporated under reduced pressure, vacuum dried and characterized (using 1H and 13C NMR and mass spectroscopy). The spectral details of the synthesized ILs are provided in the supplementary information Figs. S1 to S30.

Reference： [1]Journal of Chemical and Engineering Data,2018,vol. 63,p. 331 - 340
[2]ChemPhysChem,2016,vol. 17,p. 1006 - 1017
[3]Patent: CN105315215,2016,A .Location in patent: Paragraph 0020; 0021
[4]Journal of Chemical Sciences,2018,vol. 130
[5]Patent: CN107986961,2018,A .Location in patent: Paragraph 0035; 0038
[6]Patent: CN107986929,2018,A .Location in patent: Paragraph 0048; 0063
[7]New Journal of Chemistry,2018,vol. 42,p. 12243 - 12255
[8]Journal of Molecular Liquids,2018,vol. 268,p. 156 - 168

56
[ 13755-29-8 ]
[ 1448989-71-6 ]
[ 305-03-3 ]
C₅₄H₆₄Cl₂NO₂Ru₂S₃⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%		General procedure: In a Schlenk tube, 30 mg of [(eta6-p-MeC6H4Pri)2Ru2(SCH2R)2(SC6H4-p-OH)]Cl (R = C6H5 0.032 mmol,R = CH2C6H5 0.032 mmol, R = C6H4-p-But 0.029 mmol,R = C6H4-p-OMe 0.030 mmol) were dissolved in distilleddichloromethane (10 mL), ten equivalents of NaBF4 wereadded, and the mixture was stirred at room temperaturefor 12 h. Then the solution was filtered through a syringefilter (0.22 mum), passed through a small plug of silica gel(solvent system CH2Cl2/acetone 7:1) and transferred into another Schlenk tube containing a solution of <strong>[305-03-3]chlorambucil</strong>(2.0 equivalents) and 4-(dimethyl-amino)pyridine (1.0equivalent) in CH2Cl2 (5 mL). A solution of dicyclohexylcarbodiimide(2.0 equivalents) in CH2Cl2 (5 mL) wasadded dropwise to this mixture. The reaction was stirred atroom temperature under nitrogen atmosphere for 16 h. Thesolvent was then removed under reduced pressure, the residuedissolved in cold acetonitrile, filtered through a syringefilter, evaporated to dryness and chromatographed on silicagel (solvent system CH2Cl2/acetone 7:1). The first orangeband was collected and evaporated to give the products asorange powders.

Reference： [1]Journal of Biological Inorganic Chemistry,2016,vol. 21,p. 443 - 452

57
[ 13755-29-8 ]
[ 1448989-77-2 ]
[ 305-03-3 ]
C₅₆H₆₈Cl₂NO₂Ru₂S₃⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%		General procedure: In a Schlenk tube, 30 mg of [(eta6-p-MeC6H4Pri)2Ru2(SCH2R)2(SC6H4-p-OH)]Cl (R = C6H5 0.032 mmol,R = CH2C6H5 0.032 mmol, R = C6H4-p-But 0.029 mmol,R = C6H4-p-OMe 0.030 mmol) were dissolved in distilleddichloromethane (10 mL), ten equivalents of NaBF4 wereadded, and the mixture was stirred at room temperaturefor 12 h. Then the solution was filtered through a syringefilter (0.22 mum), passed through a small plug of silica gel(solvent system CH2Cl2/acetone 7:1) and transferred into another Schlenk tube containing a solution of <strong>[305-03-3]chlorambucil</strong>(2.0 equivalents) and 4-(dimethyl-amino)pyridine (1.0equivalent) in CH2Cl2 (5 mL). A solution of dicyclohexylcarbodiimide(2.0 equivalents) in CH2Cl2 (5 mL) wasadded dropwise to this mixture. The reaction was stirred atroom temperature under nitrogen atmosphere for 16 h. Thesolvent was then removed under reduced pressure, the residuedissolved in cold acetonitrile, filtered through a syringefilter, evaporated to dryness and chromatographed on silicagel (solvent system CH2Cl2/acetone 7:1). The first orangeband was collected and evaporated to give the products asorange powders.

Reference： [1]Journal of Biological Inorganic Chemistry,2016,vol. 21,p. 443 - 452

58
[ 13755-29-8 ]
[ 1448989-86-3 ]
[ 305-03-3 ]
C₆₂H₈₀Cl₂NO₂Ru₂S₃⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%		General procedure: In a Schlenk tube, 30 mg of [(eta6-p-MeC6H4Pri)2Ru2(SCH2R)2(SC6H4-p-OH)]Cl (R = C6H5 0.032 mmol,R = CH2C6H5 0.032 mmol, R = C6H4-p-But 0.029 mmol,R = C6H4-p-OMe 0.030 mmol) were dissolved in distilleddichloromethane (10 mL), ten equivalents of NaBF4 wereadded, and the mixture was stirred at room temperaturefor 12 h. Then the solution was filtered through a syringefilter (0.22 mum), passed through a small plug of silica gel(solvent system CH2Cl2/acetone 7:1) and transferred into another Schlenk tube containing a solution of <strong>[305-03-3]chlorambucil</strong>(2.0 equivalents) and 4-(dimethyl-amino)pyridine (1.0equivalent) in CH2Cl2 (5 mL). A solution of dicyclohexylcarbodiimide(2.0 equivalents) in CH2Cl2 (5 mL) wasadded dropwise to this mixture. The reaction was stirred atroom temperature under nitrogen atmosphere for 16 h. Thesolvent was then removed under reduced pressure, the residuedissolved in cold acetonitrile, filtered through a syringefilter, evaporated to dryness and chromatographed on silicagel (solvent system CH2Cl2/acetone 7:1). The first orangeband was collected and evaporated to give the products asorange powders.

Reference： [1]Journal of Biological Inorganic Chemistry,2016,vol. 21,p. 443 - 452

59
[ 13755-29-8 ]
[ 71026-66-9 ]
4-[[(1,1’-dimethylethoxy)carbonyl]amino]benzenediazonium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%		Stock solutions of isobutyl nitrite (0.345 M) trimethylsilyl chloride (0.345 M) and tert-butyl-4-aminophenylcarbamate (0.30 M) in 2:1 solvent mixture of dichloroethane and MeCN were prepared. At flow rates of 0.25 mL/min the solutions of trimethylsilyl chloride and isobutyl nitrite were pumped and united at a Upchurch PEEK T-mixer then immediately combined at a second T-mixer the solution of aniline. The combined flow stream was progressed into a PFA tubular reactor (internal volume 20 mL, residence time 26.7 min) maintained at 20 C. Samples of the reactor output were taken every 10 min for direct 1H-NMR analysis to assess conversion (which was consistent at 98% after the first 15 min). The bulk reactor output was collected (for 2 h) into a stirred round bottom flask containing a suspension of sodium tetrafluoroborate (1.087 g, 1.1 equiv.) in EtOH (20 mL). The suspension was evaporated and triturated with a 3:1 mixture of diethyl ether and MeCN to give a pale off white solid 2.266 g, 82%. 1H-NMR (400 MHz, DMSO-d6) delta/ppm: 10.97 (s, 1H), 8.58 (d, J = 8.0 Hz, 2Hz), 7.95 (d, J = 8.0 Hz, 2H), 1.51 (s, 9 H). 13C-NMR (101 MHz, DMSO-d6) delta/ppm: 152.3 (C), 151.5 (C), 135.5 (2 CH), 119.2 (2 CH), 103.5 (C), 82.2 (C), 28.2 (3 CH3). 19F-NMR (376 MHz, DMSO-d6) delta/ppm: 148.3 (s). IR (neat) 3308 (w), 2975 (w), 2246 (m), 1741 (m), 1579 (s), 1527 (s), 1433 (m), 1232 (s), 1154 (s), 1090 (s), 1056 (s), 1006 (s), 839 (s), 519 (s) cm-1. LC-MS (ESI) 220.2 (M+). HR-MS (ESI) calculated for C11H14N3O2 220.1086, found 220.1099 (Delta = 5.9 ppm).

Reference： [1]Molecules,2016,vol. 21

60
[ 13755-29-8 ]
[ 106-93-4 ]
[ 99163-12-9 ]
2-bromoethyl-4-(4’-formylphenyl)pyridinium tetrafluoroborate [ No CAS ]

Reference： [1]Chemistry - An Asian Journal,2016,vol. 11,p. 3258 - 3266

61
[ 13755-29-8 ]
2-bromoethyl-4-(4’-formylphenyl)pyridinium tetrafluoroborate [ No CAS ]
[ 99163-12-9 ]
2,6-bis(4-(4’-formylphenyl)-1-pyridyl)ethane tetrafluoroborate [ No CAS ]

Reference： [1]Chemistry - An Asian Journal,2016,vol. 11,p. 3258 - 3266

62
[ 13755-29-8 ]
1,2-bis(diisopropylamino)-3-chlorocyclopropenium tetrafluoroborate [ No CAS ]
[ 7650-91-1 ]
C₃₄H₄₅N₂P⁽²⁺⁾*2BF₄^(1-) [ No CAS ]

Reference： [1]Dalton Transactions,2017,vol. 46,p. 16216 - 16227

63
[ 13755-29-8 ]
[ 65039-08-9 ]
[ 143314-16-3 ]

Yield	Reaction Conditions	Operation in experiment
	In acetone; at 20℃;	In a round bottomflask, a mixture of 1-methyl imidazole (4.1 g; 50 mmol) andethyl bromide (5.45 g, 50 mmol) was stirred at 80 C in neatcondition for 10 h. After that, neutral ionic liquid [EMIM][Br]was obtained as white solid. The reactionmixturewaswashedwith ethyl acetate four times for complete removal of n-ethylbromide and other organic compounds. It was then subjected to vacuum to obtain the pure solid [EMIM][Br]. After that,sodium tetrafluoroborate (5.3 g, 48.17 mmol) was added tothe [EMIM][Br] in acetone and stirred overnight at roomtemperature to obtain [EMIM][BF4]. The solution was filteredand acetone was removed in vacuum to obtain the pure[EMIM][BF4] as a colorless liquid.
	In methanol; at 20℃; for 24h;	General procedure: Another anion exchange reaction was carried out to achieve IL with boron tetrafluorides as a counter anion (IL-BF4) by metathesis reaction as per reported literature with minor modifications (Scheme 2). A demonstrative example for the synthesis of [RMIM]BF4 (i.e., [EMIM]BF4, [BMIM]BF4, [HMIM]BF4, [OMIM]BF4, [DMIM]BF4) and [RBZMIM]BF4 (i.e., [EBZMIM]BF4, [BBZMIM]BF4, [HBZMIM]BF4, [OBZMIM]BF4, [DBZMIM]BF4) in Scheme 2 (step-3) derivatives are as follows: 1:2 ratio of the 1-methyl-3-alkylimidazolium bromide or 1-methyl-3-alkylbenzimidazolium bromide ([RBZMIM]Br) and NaBF4 were added distinctly in to the round bottom flask containing 25mL of methanol and stirred at room temperature for 24h. Afterward, the salt was removed by filtering the reaction mixture using Whatman filter paper. Further, the filtrate was centrifuged for 10min at 3000rpm to isolate the residual salts. Solvent was evaporated under reduced pressure, vacuum dried and characterized (using 1H and 13C NMR and mass spectroscopy). The spectral details of the synthesized ILs are provided in the supplementary information Figs. S1 to S30.

Reference： [1]Journal of Chemical Sciences,2018,vol. 130
[2]Journal of Molecular Liquids,2018,vol. 268,p. 156 - 168

64
[ 13755-29-8 ]
[ 4107-98-6 ]
C₃₃H₄₀N₄O [ No CAS ]
C₄₅H₅₈N₅⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

Reference： [1]Chemistry - A European Journal,2018,vol. 24,p. 7957 - 7963

65
[ 13755-29-8 ]
[ 14187-32-7 ]
C₃₃H₄₀N₄O [ No CAS ]
C₅₃H₆₃N₄O₆⁽¹⁺⁾*BF₄^(1-) [ No CAS ]

Reference： [1]Chemistry - A European Journal,2018,vol. 24,p. 7957 - 7963

66
[ 13755-29-8 ]
1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane chloride [ No CAS ]
[ 140681-55-6 ]

Reference： [1]Inorganic Chemistry,2018,vol. 57,p. 10153 - 10159

67
[ 13755-29-8 ]
[ 56-34-8 ]
[ 429-06-1 ]

Yield	Reaction Conditions	Operation in experiment
65.8%	at 20℃;	85mL 6mol / L tetraethylammonium chloride solution was added dropwise to 100mL 6mol / L sodium tetrafluoroborate solution under stirring at room temperature As the addition progressed, the solution gradually changed from clear to cloudy. After the completion of the dropwise addition, the mixture was filtered under reduced pressure, and the solid was washed with a small portion of ice water to obtain a crude salty product (92 g). The sodium chloride content was less than 1% by silver nitrate turbidimetry. (2) Purification of tetraethylammonium The step (1) to give a wet salt of the crude product 50g dispersed in the procedure of Example 4, (2) the obtained filtrate A to give a crude dispersion, at room temperature with vigorous stirring the dispersion for 15 minutes, the solid was collected by filtration under reduced pressure, the filtrate was collected standby (filtrate B), the solid was washed with ice water, -10 C - 0 C ethanol, and drained as much as possible. Then the product was placed in a vacuum drying oven at a pressure of 0.001 MPa and gradually increased from room temperature to 60 C in 12 hours. Vacuum drying, finally obtained 40g of white tetraethylammonium tetrafluoroborate solid, from the commercially available tetraethylammonium chloride raw material to the final product, the total yield is 65.8%, the detection purity is greater than 99.95%, the chloride ion content is less than 90ppm, sodium The ion content is less than 100 ppm. Repeated experiments have shown that the filtrate can replace the pure water as a dispersion to effectively increase the overall yield. This substitution can be repeated. Use at least 5 times without affecting product purity.

Reference： [1]Patent: CN108586263,2018,A .Location in patent: Paragraph 0021-0042; 0045-0052

68
[ 13755-29-8 ]
[ 113310-52-4 ]
4-(piperidin-1-yl)benzaldehyde [ No CAS ]
[ 501-65-5 ]
BF₄^(1-)*C₃₇H₃₈N₃⁽¹⁺⁾ [ No CAS ]

Reference： [1]Organic Letters,2018,vol. 20,p. 7071 - 7075

69
[ 18364-47-1 ]
[ 13755-29-8 ]
ammonium tetrafluoroborate [ No CAS ]
[ 886-66-8 ]
[ 107-06-2 ]
1-methyl-2,4-diphenyl-1H-pyrido[3,2,1-de][1,5]naphthyridin-7-ium tetrafluoroborate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2019,vol. 58,p. 254 - 258
Angew. Chem.,2019,vol. 131,p. 260 - 264,5

70
[ 13755-29-8 ]
[ 479-59-4 ]
[ 33985-71-6 ]
bis(julolidin-9-yl)methylium tetrafluoroborate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2019,vol. 2019,p. 412 - 421

71
[ 13755-29-8 ]
[ 491-34-9 ]
[ 493-50-5 ]
bis(N-methyl-1,2,3,4-tetrahydroquinolin-6-yl)methylium tetrafluoroborate [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2019,vol. 2019,p. 412 - 421

72
[ 67969-82-8 ]
[ 13755-29-8 ]
[ 14920-81-1 ]
3,3’‐oxybis(tert‐butylbenzene) [ No CAS ]
3,6‐di‐tert‐butyl‐9‐(2,6‐dimethylphenyl)xanthylium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%		General procedure: To a flame-dried 250 mL round-bottom flask under argon wereadded 4 (8.02 g, 28.4 mmol, 1 equiv), TMEDA (8.71 mL, 58.2mmol, 2.05 equiv), and anhydrous n-hexane (28 mL). Theresulting solution was cooled in an ice bath and sec-butyllithium(1.4 M solution in cyclohexane, 42.0 mL, 58.2 mmol, 2.05equiv) was added dropwise. The ice bath was removed and thereaction mixture was stirred at room temperature for 4 h. Thereaction was cooled to -78 C and a solution of methyl 2,4,6-trimethylbenzoate (5.11 g, 28.7 mmol, 1.01 equiv) in anhydrousn-hexane (28 mL) was added slowly via cannula. After the addition,the mixture was allowed to slowly warm to room temperatureand stirred for 12 h. The reaction was quenched with water(25 mL) and the biphasic mixture was stirred vigorously for 30min. The mixture was diluted with Et2O (100 mL) and the layerswere separated. The organic layer was washed with water(2 × 150 mL) and brine (1 × 150 mL). The organic layer wastransferred to a 250 mL round-bottom flask equipped with astir bar. To the vigorously stirred solution was added conc. HCl(12 mL), resulting in a bright-yellow precipitate. The suspensionwas stirred vigorously for 30 min then diluted with water (150mL). The layers were separated and the organic layer wasextracted with water (3 × 150 mL or until the washings becomecolorless). To the combined aqueous layers was added solidNaBF4 (9.35 g, 85.2 mmol, 3 equiv), resulting in a bright-yellowprecipitate. The resulting suspension was extracted withdichloromethane (3 × 150 mL or until the washings become colorless).To the combined organic layers was added HBF4·Et2Ocomplex (3.46 mL, 28.4 mmol, 1 equiv). The solution wasswirled to achieve homogeneity then washed with water(1 × 100 mL) and aq. NaBF4 (1 M, 1 × 100 mL). The organic layerwas dried over solid NaBF4, filtered, and concentrated to dryness.The residue was purified by trituration with hexanes andfiltered. The solid was rinsed with n-pentane and dried in vacuoto give xanthylium 3 (10.6 g, 21.3 mmol, 75% yield) as a yelloworangesolid.

Reference： [1]Synlett,2019,vol. 30,p. 827 - 832

73
[ 67969-82-8 ]
[ 13755-29-8 ]
[ 16633-50-4 ]
3,3’‐oxybis(tert‐butylbenzene) [ No CAS ]
3,6‐di‐tert‐butyl‐9‐(4‐fluoro‐2,6‐dimethylphenyl)xanthylium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
493 mg		General procedure: To a flame-dried 250 mL round-bottom flask under argon wereadded 4 (8.02 g, 28.4 mmol, 1 equiv), TMEDA (8.71 mL, 58.2mmol, 2.05 equiv), and anhydrous n-hexane (28 mL). Theresulting solution was cooled in an ice bath and sec-butyllithium(1.4 M solution in cyclohexane, 42.0 mL, 58.2 mmol, 2.05equiv) was added dropwise. The ice bath was removed and thereaction mixture was stirred at room temperature for 4 h. Thereaction was cooled to -78 C and a solution of methyl 2,4,6-trimethylbenzoate (5.11 g, 28.7 mmol, 1.01 equiv) in anhydrousn-hexane (28 mL) was added slowly via cannula. After the addition,the mixture was allowed to slowly warm to room temperatureand stirred for 12 h. The reaction was quenched with water(25 mL) and the biphasic mixture was stirred vigorously for 30min. The mixture was diluted with Et2O (100 mL) and the layerswere separated. The organic layer was washed with water(2 × 150 mL) and brine (1 × 150 mL). The organic layer wastransferred to a 250 mL round-bottom flask equipped with astir bar. To the vigorously stirred solution was added conc. HCl(12 mL), resulting in a bright-yellow precipitate. The suspensionwas stirred vigorously for 30 min then diluted with water (150mL). The layers were separated and the organic layer wasextracted with water (3 × 150 mL or until the washings becomecolorless). To the combined aqueous layers was added solidNaBF4 (9.35 g, 85.2 mmol, 3 equiv), resulting in a bright-yellowprecipitate. The resulting suspension was extracted withdichloromethane (3 × 150 mL or until the washings become colorless).To the combined organic layers was added HBF4·Et2Ocomplex (3.46 mL, 28.4 mmol, 1 equiv). The solution wasswirled to achieve homogeneity then washed with water(1 × 100 mL) and aq. NaBF4 (1 M, 1 × 100 mL). The organic layerwas dried over solid NaBF4, filtered, and concentrated to dryness.The residue was purified by trituration with hexanes andfiltered. The solid was rinsed with n-pentane and dried in vacuoto give xanthylium 3 (10.6 g, 21.3 mmol, 75% yield) as a yelloworangesolid.

Reference： [1]Synlett,2019,vol. 30,p. 827 - 832

74
[ 67969-82-8 ]
[ 13755-29-8 ]
[ 24085-65-2 ]
[ 14920-81-1 ]
2,7‐di‐tert‐butyl‐9‐(2,6‐dimethylphenyl)xanthylium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%		General procedure: To a flame-dried 250 mL round-bottom flask under argon wereadded 4 (8.02 g, 28.4 mmol, 1 equiv), TMEDA (8.71 mL, 58.2mmol, 2.05 equiv), and anhydrous n-hexane (28 mL). Theresulting solution was cooled in an ice bath and sec-butyllithium(1.4 M solution in cyclohexane, 42.0 mL, 58.2 mmol, 2.05equiv) was added dropwise. The ice bath was removed and thereaction mixture was stirred at room temperature for 4 h. Thereaction was cooled to -78 C and a solution of methyl 2,4,6-trimethylbenzoate (5.11 g, 28.7 mmol, 1.01 equiv) in anhydrousn-hexane (28 mL) was added slowly via cannula. After the addition,the mixture was allowed to slowly warm to room temperatureand stirred for 12 h. The reaction was quenched with water(25 mL) and the biphasic mixture was stirred vigorously for 30min. The mixture was diluted with Et2O (100 mL) and the layerswere separated. The organic layer was washed with water(2 × 150 mL) and brine (1 × 150 mL). The organic layer wastransferred to a 250 mL round-bottom flask equipped with astir bar. To the vigorously stirred solution was added conc. HCl(12 mL), resulting in a bright-yellow precipitate. The suspensionwas stirred vigorously for 30 min then diluted with water (150mL). The layers were separated and the organic layer wasextracted with water (3 × 150 mL or until the washings becomecolorless). To the combined aqueous layers was added solidNaBF4 (9.35 g, 85.2 mmol, 3 equiv), resulting in a bright-yellowprecipitate. The resulting suspension was extracted withdichloromethane (3 × 150 mL or until the washings become colorless).To the combined organic layers was added HBF4·Et2Ocomplex (3.46 mL, 28.4 mmol, 1 equiv). The solution wasswirled to achieve homogeneity then washed with water(1 × 100 mL) and aq. NaBF4 (1 M, 1 × 100 mL). The organic layerwas dried over solid NaBF4, filtered, and concentrated to dryness.The residue was purified by trituration with hexanes andfiltered. The solid was rinsed with n-pentane and dried in vacuoto give xanthylium 3 (10.6 g, 21.3 mmol, 75% yield) as a yelloworangesolid.

Reference： [1]Synlett,2019,vol. 30,p. 827 - 832

75
[ 67969-82-8 ]
[ 13755-29-8 ]
[ 14920-81-1 ]
1‐(3‐(tert‐butyl)phenoxy)naphthalene [ No CAS ]
10‐(tert‐butyl)‐7‐(2,6‐dimethylphenyl)benzo[c]xanthen‐12‐ium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1.2 g		General procedure: To a flame-dried 250 mL round-bottom flask under argon wereadded 4 (8.02 g, 28.4 mmol, 1 equiv), TMEDA (8.71 mL, 58.2mmol, 2.05 equiv), and anhydrous n-hexane (28 mL). Theresulting solution was cooled in an ice bath and sec-butyllithium(1.4 M solution in cyclohexane, 42.0 mL, 58.2 mmol, 2.05equiv) was added dropwise. The ice bath was removed and thereaction mixture was stirred at room temperature for 4 h. Thereaction was cooled to -78 C and a solution of methyl 2,4,6-trimethylbenzoate (5.11 g, 28.7 mmol, 1.01 equiv) in anhydrousn-hexane (28 mL) was added slowly via cannula. After the addition,the mixture was allowed to slowly warm to room temperatureand stirred for 12 h. The reaction was quenched with water(25 mL) and the biphasic mixture was stirred vigorously for 30min. The mixture was diluted with Et2O (100 mL) and the layerswere separated. The organic layer was washed with water(2 × 150 mL) and brine (1 × 150 mL). The organic layer wastransferred to a 250 mL round-bottom flask equipped with astir bar. To the vigorously stirred solution was added conc. HCl(12 mL), resulting in a bright-yellow precipitate. The suspensionwas stirred vigorously for 30 min then diluted with water (150mL). The layers were separated and the organic layer wasextracted with water (3 × 150 mL or until the washings becomecolorless). To the combined aqueous layers was added solidNaBF4 (9.35 g, 85.2 mmol, 3 equiv), resulting in a bright-yellowprecipitate. The resulting suspension was extracted withdichloromethane (3 × 150 mL or until the washings become colorless).To the combined organic layers was added HBF4·Et2Ocomplex (3.46 mL, 28.4 mmol, 1 equiv). The solution wasswirled to achieve homogeneity then washed with water(1 × 100 mL) and aq. NaBF4 (1 M, 1 × 100 mL). The organic layerwas dried over solid NaBF4, filtered, and concentrated to dryness.The residue was purified by trituration with hexanes andfiltered. The solid was rinsed with n-pentane and dried in vacuoto give xanthylium 3 (10.6 g, 21.3 mmol, 75% yield) as a yelloworangesolid.

Reference： [1]Synlett,2019,vol. 30,p. 827 - 832

76
[ 67969-82-8 ]
[ 13755-29-8 ]
[ 14920-81-1 ]
1‐(4‐(tert‐butyl)phenoxy)naphthalene [ No CAS ]
9‐(tert‐butyl)‐7‐(2,6‐dimethylphenyl)benzo[c]xanthen‐12‐ium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%		General procedure: To a flame-dried 250 mL round-bottom flask under argon wereadded 4 (8.02 g, 28.4 mmol, 1 equiv), TMEDA (8.71 mL, 58.2mmol, 2.05 equiv), and anhydrous n-hexane (28 mL). Theresulting solution was cooled in an ice bath and sec-butyllithium(1.4 M solution in cyclohexane, 42.0 mL, 58.2 mmol, 2.05equiv) was added dropwise. The ice bath was removed and thereaction mixture was stirred at room temperature for 4 h. Thereaction was cooled to -78 C and a solution of methyl 2,4,6-trimethylbenzoate (5.11 g, 28.7 mmol, 1.01 equiv) in anhydrousn-hexane (28 mL) was added slowly via cannula. After the addition,the mixture was allowed to slowly warm to room temperatureand stirred for 12 h. The reaction was quenched with water(25 mL) and the biphasic mixture was stirred vigorously for 30min. The mixture was diluted with Et2O (100 mL) and the layerswere separated. The organic layer was washed with water(2 × 150 mL) and brine (1 × 150 mL). The organic layer wastransferred to a 250 mL round-bottom flask equipped with astir bar. To the vigorously stirred solution was added conc. HCl(12 mL), resulting in a bright-yellow precipitate. The suspensionwas stirred vigorously for 30 min then diluted with water (150mL). The layers were separated and the organic layer wasextracted with water (3 × 150 mL or until the washings becomecolorless). To the combined aqueous layers was added solidNaBF4 (9.35 g, 85.2 mmol, 3 equiv), resulting in a bright-yellowprecipitate. The resulting suspension was extracted withdichloromethane (3 × 150 mL or until the washings become colorless).To the combined organic layers was added HBF4·Et2Ocomplex (3.46 mL, 28.4 mmol, 1 equiv). The solution wasswirled to achieve homogeneity then washed with water(1 × 100 mL) and aq. NaBF4 (1 M, 1 × 100 mL). The organic layerwas dried over solid NaBF4, filtered, and concentrated to dryness.The residue was purified by trituration with hexanes andfiltered. The solid was rinsed with n-pentane and dried in vacuoto give xanthylium 3 (10.6 g, 21.3 mmol, 75% yield) as a yelloworangesolid.

Reference： [1]Synlett,2019,vol. 30,p. 827 - 832

77
[ 13755-29-8 ]
[ 1202-34-2 ]
[ 578743-87-0 ]
[Cu(1,3-bis(-2,6-di-isopropylphenyl)imidazol-2-ylidene)(2,2'-dipyridylamine)][BF₄] [ No CAS ]

Reference： [1]Journal of Organometallic Chemistry,2019,vol. 893,p. 21 - 31

78
[ 13755-29-8 ]
[ 65039-09-0 ]
[ 143314-16-3 ]

Yield	Reaction Conditions	Operation in experiment
94%	at 40℃; for 18h;UV-irradiation;	(2) mixing the quaternary ammonium salt solution obtained in the step (1) with sodium tetrafluoroborate (the molar ratio of 1-methylimidazole to sodium tetrafluoroborate is 1:1), After heating to 40 C, Under agitation, Irradiation with ultraviolet light of 600 W/m2, The exposure time is 18h, a mixed solution containing a tetrafluoroborate ionic liquid; (3) filtering the mixture obtained in the step (2) twice, Get the filtrate, The filtrate was concentrated at 60 C. Remove ethanol, Obtaining 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid, The yield was 94%. See Table 1 for the properties of the resulting ionic liquid.

Reference： [1]Patent: CN109734668,2019,A .Location in patent: Page/Page column 9-10

79
ruthenium trichloride [ No CAS ]
[ 13755-29-8 ]
[ 17217-57-1 ]
tris(4,4'-dimethoxy-2,2'-bipyridine)ruthenium bis(tetrafluoroborate) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%		General procedure: Dried RuCl3 (0.20 g, 0.96 mmol) was dissolvedin dipropylene glycol (10 mL) and deionized water (1 mL).The solution was refluxed until the metal salt was dissolved,obtaining a dark green solution. Bipyridine (0.469 g; 3.0 mmol) wasadded, resulting in a brown solution. Ascorbic acid (0.177 g,1.0 mmol) was then added and the solution refluxed for 20 min at250 C, the brown colour changing to red. After cooling, the solutionwas diluted to 40 mL and the pH adjusted to 8 by addition of afew drops of NaOH solution (2.5 M). NaBF4 (4.0 g, 36 mmol) wasadded and the solution cooled on ice. After vacuum filtration,washing with cold water, and drying, 0.329 g [Ru(bpy)3](BF4)2product was obtained.

Reference： [1]Electrochimica Acta,2019,vol. 320

80
ruthenium trichloride [ No CAS ]
[ 13755-29-8 ]
[ 92149-07-0 ]
tris(4,7-dimethoxy-1,10-phenanthroline)ruthenium bis(tetrafluoroborate) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%		General procedure: Dried RuCl3 (0.20 g, 0.96 mmol) was dissolvedin dipropylene glycol (10 mL) and deionized water (1 mL).The solution was refluxed until the metal salt was dissolved,obtaining a dark green solution. Bipyridine (0.469 g; 3.0 mmol) wasadded, resulting in a brown solution. Ascorbic acid (0.177 g,1.0 mmol) was then added and the solution refluxed for 20 min at250 C, the brown colour changing to red. After cooling, the solutionwas diluted to 40 mL and the pH adjusted to 8 by addition of afew drops of NaOH solution (2.5 M). NaBF4 (4.0 g, 36 mmol) wasadded and the solution cooled on ice. After vacuum filtration,washing with cold water, and drying, 0.329 g [Ru(bpy)3](BF4)2product was obtained.

Reference： [1]Electrochimica Acta,2019,vol. 320

81
ruthenium trichloride [ No CAS ]
[ 13755-29-8 ]
[ 18511-72-3 ]
tris(4,4'-dinitro-2,2'-bipyridine)ruthenium bis(tetrafluoroborate) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70.12%		General procedure: Dried RuCl3 (0.20 g, 0.96 mmol) was dissolvedin dipropylene glycol (10 mL) and deionized water (1 mL).The solution was refluxed until the metal salt was dissolved,obtaining a dark green solution. Bipyridine (0.469 g; 3.0 mmol) wasadded, resulting in a brown solution. Ascorbic acid (0.177 g,1.0 mmol) was then added and the solution refluxed for 20 min at250 C, the brown colour changing to red. After cooling, the solutionwas diluted to 40 mL and the pH adjusted to 8 by addition of afew drops of NaOH solution (2.5 M). NaBF4 (4.0 g, 36 mmol) wasadded and the solution cooled on ice. After vacuum filtration,washing with cold water, and drying, 0.329 g [Ru(bpy)3](BF4)2product was obtained.

Reference： [1]Electrochimica Acta,2019,vol. 320

82
[ 13755-29-8 ]
[ 31599-59-4 ]
[ 57002-01-4 ]
(E)-(2-cyclohexylvinyl)(2-methylphenyl)iodonium tetrafluoroborate [ No CAS ]

Reference： [1]Chemistry - A European Journal,2019,vol. 25,p. 10823 - 10827

83
[ 34784-02-6 ]
[ 13755-29-8 ]
[ 34686-76-5 ]
(E)-3-bromo-2-(hex-2-en-1-yl)isoquinolin-2-ium tetrafluoroborate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2019,vol. 58,p. 14104 - 14109
Angew. Chem.,2019,vol. 131,p. 14242 - 14247,6

84
[ 13755-29-8 ]
[ 938-33-0 ]
[ 34686-76-5 ]
(E)-1-(hex-2-en-1-yl)-8-methoxyquinolin-1-ium tetrafluoroborate [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2019,vol. 58,p. 14104 - 14109
Angew. Chem.,2019,vol. 131,p. 14242 - 14247,6

85
tetrafluoroboric acid [ No CAS ]
[ 13755-29-8 ]
[ 14691-89-5 ]
4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
3 g	With sodium hypochlorite;	In a 15 mm flame-dried round bottom flask equipped with a magnetic stir bar, 4-AcNH-TEMPO + BF4- (2.0 equiv, 20 mmol, 6.0 g), and NH4OAc (4.0 equiv, 40 mmol) , 3.2 g) was evacuated (introduced) and then refilled with nitrogen (repeat 3 times).After addition of 10 mL of AcOH, octanal (10 mmol, 1.6 mL) and AcOH (10 mL) were added sequentially.The reaction mixture was stirred for 12 h at 70 C. under an N 2 balloon and then cooled at room temperature.The reaction was diluted with EtOAc and extracted with 4M aqueous HCl solution.An aqueous Na 2 CO 3 solution was added to the obtained aqueous layer.The aqueous mixture was extracted with EtOAc.The dark red solution was separated, dried over MgSO 4, filtered and concentrated in vacuo. An orange-white solid was obtained which was crude 4-AcNH-TEMPO.Oxidation of the crude 4-AcNH-TEMPO with HBF 4, NaOCl, and NaBF 4 produces 4-AcNH-TEMPO + BF 4-.50% (3.0 g) of 4-AcNH-TEMPO + BF4-regenerated after filtration was obtained.Purity of regenerated 4-AcNH-TEMPO+ BF4- was analyzed by 1H NMR spectrum in CF 3 COOD (melting point 185-186 C.).

Reference： [1]Patent: KR2019/106583,2019,A .Location in patent: Paragraph 0077-0088; 0151-0152

86
[ 13755-29-8 ]
ytterbium(III) chloride [ No CAS ]
erbium(III) chloride [ No CAS ]
calcium(II) chloride dihydrate [ No CAS ]
manganese(II) chloride tetrahydrate [ No CAS ]
[ 6132-04-3 ]
Ca₀₆₆₁Yb₀₁₄₈Er_0.02Mn₀₀₀₇Na_16.4F₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: Firstly, the suitable RE oxides were dissolved in ultra-pure chloric acid, then RECl3 synthesized were diluted with distilled water and 0.5M solutions of YbCl3, ErCl3 were obtained. The solutions were evaporated three times in order to remove the excess of the acid. The 0.5M solutions of MnCl2, CaCl2 and NaBF4 were also prepared. Four mmols of <strong>[6132-04-3]sodium citrate tribasic dihydrate</strong> were dissolved in distilled water and mixed with stoichiometric volume of CaCl2 solution upon stirring (solution A). Next the desired amounts of RECl3 and MnCl2 solutions (solution B) were mixed.Then, solution B was dropwise added to the solution A. Then, to thus prepared mixture, a fluoride source was added (4 mmol), still upon continuous stirring. The prepared mixture had a volume of about 20 ml and was filled with 10 cm3 distilled water to obtain a series of solutions of the same volume, which ensured the same pressure in each vessel. The pH was not set using additional reagents,but the procedure applied implied similar pH ~6.7 of each sample. The amounts of the reagents used were calculated assuming that the final product molar amount would be 2 mmol. Finally, the obtained transparent solutions were placed in Teflon vessels and put in an autoclave. After synthesis the reactor was left to cool down. The as-obtained products were collected by centrifugation, washed firstly with water then with ethanol three times and dried at 70 C for 12 h in air. White powders were grounded in a mortar and then analysed.

Reference： [1]Journal of Alloys and Compounds,2020,vol. 817

87
[ 13755-29-8 ]
ytterbium(III) chloride [ No CAS ]
erbium(III) chloride [ No CAS ]
calcium(II) chloride dihydrate [ No CAS ]
manganese(II) chloride tetrahydrate [ No CAS ]
[ 6132-04-3 ]
Ca₀₆₄₅Yb₀₁₅₂Er₀₀₂₁Mn₀₀₂₆Na₀₁₅₆F_2.02 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: Firstly, the suitable RE oxides were dissolved in ultra-pure chloric acid, then RECl3 synthesized were diluted with distilled water and 0.5M solutions of YbCl3, ErCl3 were obtained. The solutions were evaporated three times in order to remove the excess of the acid. The 0.5M solutions of MnCl2, CaCl2 and NaBF4 were also prepared. Four mmols of <strong>[6132-04-3]sodium citrate tribasic dihydrate</strong> were dissolved in distilled water and mixed with stoichiometric volume of CaCl2 solution upon stirring (solution A). Next the desired amounts of RECl3 and MnCl2 solutions (solution B) were mixed.Then, solution B was dropwise added to the solution A. Then, to thus prepared mixture, a fluoride source was added (4 mmol), still upon continuous stirring. The prepared mixture had a volume of about 20 ml and was filled with 10 cm3 distilled water to obtain a series of solutions of the same volume, which ensured the same pressure in each vessel. The pH was not set using additional reagents,but the procedure applied implied similar pH ~6.7 of each sample. The amounts of the reagents used were calculated assuming that the final product molar amount would be 2 mmol. Finally, the obtained transparent solutions were placed in Teflon vessels and put in an autoclave. After synthesis the reactor was left to cool down. The as-obtained products were collected by centrifugation, washed firstly with water then with ethanol three times and dried at 70 C for 12 h in air. White powders were grounded in a mortar and then analysed.

Reference： [1]Journal of Alloys and Compounds,2020,vol. 817

88
[ 13755-29-8 ]
ytterbium(III) chloride [ No CAS ]
erbium(III) chloride [ No CAS ]
calcium(II) chloride dihydrate [ No CAS ]
manganese(II) chloride tetrahydrate [ No CAS ]
[ 6132-04-3 ]
Ca₀₆₁₆Yb₀₁₅₆Er_0.02Mn₀₀₄₇Na₀₁₆₁F_2.01 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: Firstly, the suitable RE oxides were dissolved in ultra-pure chloric acid, then RECl3 synthesized were diluted with distilled water and 0.5M solutions of YbCl3, ErCl3 were obtained. The solutions were evaporated three times in order to remove the excess of the acid. The 0.5M solutions of MnCl2, CaCl2 and NaBF4 were also prepared. Four mmols of <strong>[6132-04-3]sodium citrate tribasic dihydrate</strong> were dissolved in distilled water and mixed with stoichiometric volume of CaCl2 solution upon stirring (solution A). Next the desired amounts of RECl3 and MnCl2 solutions (solution B) were mixed.Then, solution B was dropwise added to the solution A. Then, to thus prepared mixture, a fluoride source was added (4 mmol), still upon continuous stirring. The prepared mixture had a volume of about 20 ml and was filled with 10 cm3 distilled water to obtain a series of solutions of the same volume, which ensured the same pressure in each vessel. The pH was not set using additional reagents,but the procedure applied implied similar pH ~6.7 of each sample. The amounts of the reagents used were calculated assuming that the final product molar amount would be 2 mmol. Finally, the obtained transparent solutions were placed in Teflon vessels and put in an autoclave. After synthesis the reactor was left to cool down. The as-obtained products were collected by centrifugation, washed firstly with water then with ethanol three times and dried at 70 C for 12 h in air. White powders were grounded in a mortar and then analysed.

Reference： [1]Journal of Alloys and Compounds,2020,vol. 817

89
[ 13755-29-8 ]
ytterbium(III) chloride [ No CAS ]
erbium(III) chloride [ No CAS ]
calcium(II) chloride dihydrate [ No CAS ]
manganese(II) chloride tetrahydrate [ No CAS ]
[ 6132-04-3 ]
Ca₀₅₉₉Yb₀₁₆₆Er₀₀₂₃Mn_0.06Na₀₁₅₂F_2.04 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: Firstly, the suitable RE oxides were dissolved in ultra-pure chloric acid, then RECl3 synthesized were diluted with distilled water and 0.5M solutions of YbCl3, ErCl3 were obtained. The solutions were evaporated three times in order to remove the excess of the acid. The 0.5M solutions of MnCl2, CaCl2 and NaBF4 were also prepared. Four mmols of <strong>[6132-04-3]sodium citrate tribasic dihydrate</strong> were dissolved in distilled water and mixed with stoichiometric volume of CaCl2 solution upon stirring (solution A). Next the desired amounts of RECl3 and MnCl2 solutions (solution B) were mixed.Then, solution B was dropwise added to the solution A. Then, to thus prepared mixture, a fluoride source was added (4 mmol), still upon continuous stirring. The prepared mixture had a volume of about 20 ml and was filled with 10 cm3 distilled water to obtain a series of solutions of the same volume, which ensured the same pressure in each vessel. The pH was not set using additional reagents,but the procedure applied implied similar pH ~6.7 of each sample. The amounts of the reagents used were calculated assuming that the final product molar amount would be 2 mmol. Finally, the obtained transparent solutions were placed in Teflon vessels and put in an autoclave. After synthesis the reactor was left to cool down. The as-obtained products were collected by centrifugation, washed firstly with water then with ethanol three times and dried at 70 C for 12 h in air. White powders were grounded in a mortar and then analysed.

Reference： [1]Journal of Alloys and Compounds,2020,vol. 817

90
[ 13755-29-8 ]
ytterbium(III) chloride [ No CAS ]
erbium(III) chloride [ No CAS ]
calcium(II) chloride dihydrate [ No CAS ]
manganese(II) chloride tetrahydrate [ No CAS ]
[ 6132-04-3 ]
Ca₀₅₃₇Yb_0.19Er₀₀₂₆Mn_0.07Na₀₁₇₇F_2.04 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: Firstly, the suitable RE oxides were dissolved in ultra-pure chloric acid, then RECl3 synthesized were diluted with distilled water and 0.5M solutions of YbCl3, ErCl3 were obtained. The solutions were evaporated three times in order to remove the excess of the acid. The 0.5M solutions of MnCl2, CaCl2 and NaBF4 were also prepared. Four mmols of <strong>[6132-04-3]sodium citrate tribasic dihydrate</strong> were dissolved in distilled water and mixed with stoichiometric volume of CaCl2 solution upon stirring (solution A). Next the desired amounts of RECl3 and MnCl2 solutions (solution B) were mixed.Then, solution B was dropwise added to the solution A. Then, to thus prepared mixture, a fluoride source was added (4 mmol), still upon continuous stirring. The prepared mixture had a volume of about 20 ml and was filled with 10 cm3 distilled water to obtain a series of solutions of the same volume, which ensured the same pressure in each vessel. The pH was not set using additional reagents,but the procedure applied implied similar pH ~6.7 of each sample. The amounts of the reagents used were calculated assuming that the final product molar amount would be 2 mmol. Finally, the obtained transparent solutions were placed in Teflon vessels and put in an autoclave. After synthesis the reactor was left to cool down. The as-obtained products were collected by centrifugation, washed firstly with water then with ethanol three times and dried at 70 C for 12 h in air. White powders were grounded in a mortar and then analysed.

Reference： [1]Journal of Alloys and Compounds,2020,vol. 817

91
[ 13755-29-8 ]
ytterbium(III) chloride [ No CAS ]
erbium(III) chloride [ No CAS ]
calcium(II) chloride dihydrate [ No CAS ]
[ 6132-04-3 ]
Ca_0.68Yb₀₁₄₉Er₀₀₁₉Na₀₁₅₃F_2.02 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: Firstly, the suitable RE oxides were dissolved in ultra-pure chloric acid, then RECl3 synthesized were diluted with distilled water and 0.5M solutions of YbCl3, ErCl3 were obtained. The solutions were evaporated three times in order to remove the excess of the acid. The 0.5M solutions of MnCl2, CaCl2 and NaBF4 were also prepared. Four mmols of <strong>[6132-04-3]sodium citrate tribasic dihydrate</strong> were dissolved in distilled water and mixed with stoichiometric volume of CaCl2 solution upon stirring (solution A). Next the desired amounts of RECl3 and MnCl2 solutions (solution B) were mixed.Then, solution B was dropwise added to the solution A. Then, to thus prepared mixture, a fluoride source was added (4 mmol), still upon continuous stirring. The prepared mixture had a volume of about 20 ml and was filled with 10 cm3 distilled water to obtain a series of solutions of the same volume, which ensured the same pressure in each vessel. The pH was not set using additional reagents,but the procedure applied implied similar pH ~6.7 of each sample. The amounts of the reagents used were calculated assuming that the final product molar amount would be 2 mmol. Finally, the obtained transparent solutions were placed in Teflon vessels and put in an autoclave. After synthesis the reactor was left to cool down. The as-obtained products were collected by centrifugation, washed firstly with water then with ethanol three times and dried at 70 C for 12 h in air. White powders were grounded in a mortar and then analysed.

Reference： [1]Journal of Alloys and Compounds,2020,vol. 817

92
[ 616-47-7 ]
[ 13755-29-8 ]
[ 111-25-1 ]
[ 244193-50-8 ]

Reference： [1]Journal of Materials Chemistry C,2020,vol. 8,p. 2899 - 2912

93
[ 13755-29-8 ]
[ 2362-50-7 ]
[ 14850-23-8 ]
C₂₀H₂₃S₂⁽¹⁺⁾*BF₄^(1-) [ No CAS ]