Structure of Ethylenebis(diphenylphosphine)
CAS No.: 1663-45-2
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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Phosphine‐Ligated Cobalt (II) Acetylacetonate Complexes
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.
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Keywords: Cobalt ; Phosphines ; Acetylacetonate Complexes ; Paramagnetic NMR ; Clusters
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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.
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Keywords: copper(I) iodide coordination polymers ; photophysics ; TADF
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Purchased from AmBeed: 1663-45-2 ; 7688-25-7 ; 2071-20-7 ; 27721-02-4 ; 19845-69-3 ; 6737-42-4 ; 4549-31-9 ; 7681-65-4 ; 41625-30-3
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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 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H332-H335 |
Precautionary Statements: | P261-P280-P305+P351+P338 |
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 |
27.18 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
4.39 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
5.87 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
5.25 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
6.69 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
8.15 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
6.07 |
Log S (ESOL):? ESOL: Topological method implemented from |
-6.18 |
Solubility | 0.000263 mg/ml ; 0.00000066 mol/l |
Class? Solubility class: Log S scale |
Poorly soluble |
Log S (Ali)? Ali: Topological method implemented from |
-6.21 |
Solubility | 0.000244 mg/ml ; 0.000000612 mol/l |
Class? Solubility class: Log S scale |
Poorly soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-10.9 |
Solubility | 0.000000005 mg/ml ; 0.0 mol/l |
Class? Solubility class: Log S scale |
Insoluble |
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) |
Yes |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
Yes |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
Yes |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
Yes |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-4.56 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
1.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
1.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
1.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<2.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
5.2 |
* 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.
Yield | Reaction Conditions | Operation 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. |