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Chemical Structure| 1663-45-2 Chemical Structure| 1663-45-2

Structure of Ethylenebis(diphenylphosphine)
CAS No.: 1663-45-2

Chemical Structure| 1663-45-2

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Jayawardhena, JPI Dulmini ; Krause, Jeanette A ; Guan, Hairong ;

Abstract: Cobalt(II) acetylacetonate complexes bearing a phosphine ligand can be key intermediates or precursors to cobalt-based catalysts; however, they have been rarely studied, especially from the molecular structure point of view. This work is focused on the understanding of how different phosphines react with Co(acac)2 (acac = acetylacetonate). To do so, a variety of analytical tools including NMR and IR spectroscopy, X-ray crystallography, mass spectrometry, and elemental analysis have been used to study the reactions and characterize the isolated products. These results have shown that the monodentate ligand, HPPh2, binds to Co(acac)2 weakly and reversibly to produce Co2(acac)4(HPPh2), whereas the bidentate ligand, 1,2-bis(diphenylphosphino)ethane (dppe), interacts with Co(acac)2 more strongly to yield a one-dimensional coordination polymer of Co(acac)2(dppe). 2-(Dicyclohexylphosphino)methyl-1Hpyrrole (CyPNH), which is a pyrrole-tethered phosphine, forms an unusual 5-coordinate cobalt complex, Co(acac)2(CyPNH), in which the pyrrole moiety participates in a bifurcated hydrogen-bonding interaction with the [acac] – ligands. In contrast, another bidentate ligand, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), fails to react with Co(acac)2, presumably due to its wide bite angle and difficulty in bridging two metals.

Keywords: Cobalt ; Phosphines ; Acetylacetonate Complexes ; Paramagnetic NMR ; Clusters

Purchased from AmBeed: ; ;

Boivin, Leo ; Schlachter, Adrien ; Fortin, Daniel ; Lescop, Christophe ; Harvey, Pierre D. ;

Abstract: The prediction of the metal cluster within a coordination polymer or complex, as well as the dimensionality of the resulting polymer or complex (i.e., 0D, 1D, 2D, or 3D), is often challenging. This is the case for Ph2P(CH2)mPPh2 ligands (1 ≤ m ≤ 8) and CuX salts, particularly for X = I. This work endeavors a systematic statistical anal. combining studies in the literature and new data, mapping the nature of the resulting CuI aggregates with eight different diphoshphines in 2:1, 3:2, 1:1, 2:3, and 1:2 CuI:Ph2P(CH2)mPPh2 molar ratios as a function of m, which lead to either pure products or mixtures Several trends are made relating stoichiometry and chain length to the CuI cluster formed (i.e., globular vs. quasi-planar). Four new X-ray structures were determined: [Cu3I2(L1)3]I, Cu3I3(L2)2, Cu2I2(L6)2, and Cu4I4(L8)2, where m is, resp., 1, 2, 6, and 8, in which the CuxIy central aggregates adopt triangular bipyramid, diamond, rhomboid, and cubane shaped motifs, resp. Photophys. measurements assisted the establishment of trends considering the paucity of the crystallog. structures. During this study, it was also found that the 0D-complex Cu2I2(Ph2P(CH2)5PPh2)2 exhibits thermally activated delayed fluorescence.

Keywords: copper(I) iodide coordination polymers ; photophysics ; TADF

Purchased from AmBeed: ; ; ; ; ; ; ; ;

Alternative Products

Product Details of [ 1663-45-2 ]

CAS No. :1663-45-2
Formula : C26H24P2
M.W : 398.42
SMILES Code : P(CCP(C1=CC=CC=C1)C2=CC=CC=C2)(C3=CC=CC=C3)C4=CC=CC=C4
MDL No. :MFCD00003047
InChI Key :QFMZQPDHXULLKC-UHFFFAOYSA-N
Pubchem ID :74267

Safety of [ 1663-45-2 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H332-H335
Precautionary Statements:P261-P280-P305+P351+P338

Computational Chemistry of [ 1663-45-2 ] Show Less

Physicochemical Properties

Num. heavy atoms 28
Num. arom. heavy atoms 24
Fraction Csp3 0.08
Num. rotatable bonds 7
Num. H-bond acceptors 0.0
Num. H-bond donors 0.0
Molar Refractivity 127.76
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

27.18 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

4.39
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

5.87
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

5.25
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

6.69
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

8.15
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

6.07

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-6.18
Solubility 0.000263 mg/ml ; 0.00000066 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Poorly soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-6.21
Solubility 0.000244 mg/ml ; 0.000000612 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Poorly soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-10.9
Solubility 0.000000005 mg/ml ; 0.0 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Insoluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

High
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

Yes
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

Yes
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

Yes
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

Yes
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-4.56 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

1.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

1.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

1.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<2.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

5.2

Application In Synthesis of [ 1663-45-2 ]

* 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.

  • Downstream synthetic route of [ 1663-45-2 ]

[ 1663-45-2 ] Synthesis Path-Downstream   1~12

  • 1
  • [ 52522-40-4 ]
  • [ 1663-45-2 ]
  • [ 212518-93-9 ]
  • 2
  • [ 52522-40-4 ]
  • [ 1830-54-2 ]
  • [ 1663-45-2 ]
  • [ 524942-56-1 ]
  • 4
  • [ 52522-40-4 ]
  • [ 72343-39-6 ]
  • [ 1663-45-2 ]
  • [ 257300-33-7 ]
  • [ 257300-33-7 ]
  • 5
  • [ 52522-40-4 ]
  • 2,2-Dimethyl-5-chlor-hexin-3 [ No CAS ]
  • [ 1663-45-2 ]
  • [ 257300-31-5 ]
  • 6
  • [ 52522-40-4 ]
  • 2,2-Dimethyl-5-chlor-hexin-3 [ No CAS ]
  • [ 1663-45-2 ]
  • [ 257300-31-5 ]
  • [ 257300-31-5 ]
  • 7
  • [ 52522-40-4 ]
  • [ 2926-30-9 ]
  • [ 1663-45-2 ]
  • [ 257300-25-7 ]
  • Pd(C4H9CCCHCH3)(C26H24P2)(1+)*O3SCF3(1-)*CH2Cl2 = [Pd(C4H9CCCHCH3)(C26H24P2)]O3SCF3*CH2Cl2 [ No CAS ]
  • 8
  • [ 26305-75-9 ]
  • [ 90076-65-6 ]
  • [ 1663-45-2 ]
  • [ 904285-67-2 ]
  • 9
  • [ 27148-03-4 ]
  • bis(acetylacetonato)palladium(II) [ No CAS ]
  • [ 75-05-8 ]
  • [ 1663-45-2 ]
  • [ 1223049-00-0 ]
  • Pd2(C6H4CSNSO2)2(CH2P(C6H5)2)4 [ No CAS ]
  • 10
  • [ 27148-03-4 ]
  • [ 64-17-5 ]
  • [ 13453-07-1 ]
  • [ 1663-45-2 ]
  • μ-bis(diphenylphosphino)ethane-κP,P'-bis[(1,1-dioxide-1,2-benzoisothiazol-3-thionato-κS) gold(I)] solvato ethanol [ No CAS ]
  • 11
  • [(η5-C5H5)Fe(1,2-bis(diphenylphosphino)ethane)(N4CC6H4NO2)] [ No CAS ]
  • [ 16687-60-8 ]
  • [ 542-92-7 ]
  • [ 1663-45-2 ]
  • 12
  • [ 52522-40-4 ]
  • [ 1663-45-2 ]
  • [ 23055-10-9 ]
  • C32H32O4P2Pd [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% In acetone; for 1h;Inert atmosphere; 0.1624 g (0.4076 mmol) of 1,2-bis(diphenylphosphine)ethane, 0.1671 g (1.159 mmol) of dmfu and 0.2002 g (0.1934 mmol) of [Pd2(DBA)3*CHCl3] were dissolved under inert atmosphere (Ar) in 30 ml of anhydrous acetone and vigorously stirred for 60 min. Owing to the progressive dissolution of [Pd2(DBA)3*CHCl3], the violet color of the mixture gradually disappeared and the concomitant precipitation of the scarcely soluble pale yellow complex 1j was observed. The solution was dried under vacuum, the residue dissolved in CH2Cl2, treated with activated charcoal and filtered on a celite filter. The clear pale yellow solution was concentrated under vacuum and the title complex precipitated by slow addition of diethylether. Complex 1j was filtered off on a gooch, washed with diethylether and dried under vacuum. 0.2027 g (yield 81percent) of the title complex 1j as a pale yellow solid was obtained. 1H NMR (300 MHz, CDCl3, T = 298 K, ppm) delta: 2.11-2.61 (m, 4H, CH2P), 3.40 (s, 3H, OCH3), 4.33-4.42 (m, 2H, CH=CH), 7.32-7.53 (m, 16H, PPh), 7.79-7.85 (m, 4H, PPh). 13C{1H} NMR (CDCl3, T = 298 K, ppm selected peaks) delta: 26.7 (m CH2, CH2P), 50.5 (CH3, OCH3), 52.9 (m, CH, CH=CH), 173.7 (C, CO). 31P{1H} NMR (CD2Cl2, T = 298 K, ppm) delta: 39.0. IR (KBr, pellet, cm-1): 1683 (nCO). Anal. Calcd. for C32H32O4P2Pd: C 59.22, H 4.97. Found: C 59.11, H 5.03.
 

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