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Some new organometallics of ruthenium(II) of the type [RuCl2(COD)(CO)L] (1a-f) and [RuCl2(COD)L2] (2a-f) (where L is substituted tertiary phosphines), have been synthesized by using precursors [RuCl2(COD)(CO)(CH3CN)] (1) and [RuCl2(COD)(CH3CN)2] (2) with the substituted tertiary phosphine ligands in 1:1 and 1:2 molar ratio. The organometallics (2a-f) have been further reacted with carbonmonoxide to produce compounds of the type [RuCl2(CO)L2] (3a-f). These compounds were characterized by elemental analysis, IR, NMR (1H, 13C and 31P), mass and electronic spectral data. The catalytic activity of all these organometallics were studied and found that they are efficient catalysts for hydrolysis of etofibrate. The hydrolyzed product was separated by column chromatography and the percent yields are found in the range of 98.6-99.1%.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A series of bidentate phosphorus-nitrogen ligands was synthesised for the palladium-catalysed reductive carbonylation of nitrobenzene in order to combine the favourable influence of the phosphorus atom on the stability of the catalyst complex with the stimulating effect of the nitrogen atom on the catalytic activity. The nitrogen atom of the P/N ligand was either incorporated in an imine function, yielding the JV-(2?-diphenylphosphinobenzylidene)-R-amine ligands (R = phenyl, 4-chlorophenyl, 2,4-dimethoxyphenyl, 2,4-dimethylphenyl, tert-butyl), or in a heteroaromatic ring system which gave 2-(2?-(diphenylphosphino)ethyl)pyridine and 8-(diphenylphosphino)quinoline. Complexes of the type Pd(ligand)2(BF4)2 were prepared for these ligands. Additionally, a series of bidentate phosphorus ligands was tested: dppm, dppe, dppp, dppb, dppf, 1,2-bis(diphenylphosphino)benzene, 1,8-bis(diphenylphosphino)naphthalene, bis(2-diphenylphosphinophenyl)ether, and 9,9-dimethyl-4,6-bis(diphenylphosphino)xanthene. The P/N ligands containing the imine function did not yield any conversion of the nitrobenzene in combination with Pd. On the use of the second type of P/N ligand, moderately active palladium catalysts were obtained. This different behaviour is ascribed to the relatively low pi *-level of the imine-containing ligands. Oxidation of the phosphorus donor atom by the nitro substrate inactivated the catalysts derived from the P/N ligands as well as from a series of P/P ligands. For the bidentate phosphorus ligands the bite angle and flexibility of the ligand turned out to be of crucial influence due to the different geometries required for the Pd(II) and Pd(0) intermediates of the catalytic cycle.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A joint effort: A novel, highly efficient, and selective procedure for phosphane modification of proteins is reported (see scheme). This method involves cysteine modification with a maleimide containing a hydrazide functional group and subsequent hydrazone formation with phosphane aldehydes. Mono- and bidentate phosphane ligands were successfully coupled to several proteins, one of which was coordinated to rhodium to give an artificial metalloenzyme.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The addition of 1 and 2 equivalents of AlMe3 to cis,cis-C 6H9(NHCH2C6H4-o-R) 3 (R = PPh2 (3) and SPh (4)) gives complexes [cis,cis-C6H9(NCH2C6H 4-o-R-kappaN)2(NHCH2C6H 4-o-R-kappaN)]AlMe (R = PPh2 (7) and SPh (8)) and [cis,cis-C6H9(NCH2C6H 4-o-R)3-kappa5mu2N]Al 2Me3 (R = PPh2 (5) and SPh (6)), respectively. The bimetallic complexes are active in the polymerization of epsilon-caprolactone and rac-lactide whereas the monometallic complexes are not, although no cooperative behaviour is observed between the two aluminium atoms of 5 and 6. The polycaprolactone samples, which were characterized using 1H NMR, MALDI-TOF, and SEC, show the presence of residual ligands 3 or 4 bound to the polymer and the in situ NMR studies confirm that the insertion occurs in an Al-N bond.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Treating C60 with o-(diphenylphosphino)benzaldehyde and o-aminomethylpyridine in refluxing o-dichlorobenzene affords a new fullerene derivative syn-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60) (1) in moderate yield. Compound 1 displays versatile coordination modes. Such that, reactions of 1 with Os3(CO)11(NCMe), W(CO)4(NCMe)2, and Ru3(CO)12 produce Os3(CO)11(eta1-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (2), W(CO)4(eta2-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (3), and Ru(CO)3(eta3-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (4), respectively. Interestingly, heating 4 with Ru3(CO)12 leads to transfer of the fullerene addend to give C60 and a tetraruthenium cluster complex (mu-H)Ru4(CO)11(mu4,eta4-PPh2(o-C6H4)CH2NC(o-C5H4N)) (5). The structures of 1 and 5 have been determined by an X-ray diffraction study.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Treating C60 with o-(diphenylphosphino)benzaldehyde and o-aminomethylpyridine in refluxing o-dichlorobenzene affords a new fullerene derivative syn-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60) (1) in moderate yield. Compound 1 displays versatile coordination modes. Such that, reactions of 1 with Os3(CO)11(NCMe), W(CO)4(NCMe)2, and Ru3(CO)12 produce Os3(CO)11(eta1-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (2), W(CO)4(eta2-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (3), and Ru(CO)3(eta3-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (4), respectively. Interestingly, heating 4 with Ru3(CO)12 leads to transfer of the fullerene addend to give C60 and a tetraruthenium cluster complex (mu-H)Ru4(CO)11(mu4,eta4-PPh2(o-C6H4)CH2NC(o-C5H4N)) (5). The structures of 1 and 5 have been determined by an X-ray diffraction study.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Compounds of the formulae I and Ia in the form of mixtures of diastereomers or pure diastereomers, (I), (Ia), where R1 is a hydrogen atom or C1-C4-alkyl and R’1 is C1-C4-alkyl; X1 and X2 are each, independently of one another, a sec-phosphino group; T is C6-C20-arylene or C4-C18- heteroarylene having heteroatoms selected from the group consisting of O, S, -N= and N(C1-C4-alkyl); v is 0 or an integer from 1 to 4; X1 is bound in the ortho position relative to the T-C* bond; Q is vinyl, methyl, ethyl, -CH2-OR, -CH2-N(C1-C4-alkyl)2 or a C- or S-bonded chiral group which directs metals of metallation reagents into the ortho position; R is hydrogen, a silyl radical or an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic hydrocarbon radical which has from 1 to 18 carbon atoms and is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, F or CF3; are ligands for metal complexes as homogeneous catalyst in asymmetric syntheses.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Hydrocarbon solutions of PtPCy3(C2H4)2 (Cy = cyclohexyl) react rapidly with 8-quinolinecarboxaldehyde (1 equiv.) to yield tricyclohexylphosphine quinoline-carboxyl platinum hydride (1) and CH2CH2 (2 equiv.).Compound 1 reacts with CCl4 in hydrocarbons to give PtPCy3(NC9H6CO)Cl (2) and CHCl3.The compound PtPCy3(C2H4)2 also reacts with Ph2P(C6H4-o-CHO) and Ph2As(C6H4-o-CHO) to give PCy3PtPh2P(C6H4-o-CO)(H) (3) and PCy3PtPh2As(C6H4-o-CO)(H) (4), respectively.Compounds 1, 2, 3, and 4 were characterized by infrared and 1H NMR spectra, and the crystal structure of 3 was determined by X-ray diffraction.Crystals of 3 are monoclinic, with space group P21/n and Z = 4 with the unit cell dimensions a 9.7936(17), b 14.844(35), c 23.530(64) Angstroem, beta 91.817 (18)deg, and V 3419.09(1.36) Angstroem3.The structure is refined to final discrepancy factors of R = 0.055, and Rw = 0.064.The molecular structure of 3 is that ligating atoms are in a plane containing Pt.The position of the hydride was not located crystallographically, but the 1H NMR spectrum of 3, supports the presence of a terminal hydride that is cis to the carbonyl.The IR band of 3 at 2023 cm-1, which is assigned to nu(Pt-H), and the hydride cleavage reaction of 1 with CCl4, provide evidence for the Pt-H bond.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

A new application about 2-(Diphenylphosphino)benzaldehyde

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Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn’t involve a screen. 50777-76-9, C19H15OP. A document type is Article, introducing its new discovery., HPLC of Formula: C19H15OP

Chromium-based complexes are among the most important catalysts in the field of ethylene polymerization and oligomerization. Heterogeneous Cr Phillips catalysts account for more than one-third of the commercialized high density polyethylene (HDPE). In this contribution, chromium complexes, LCrCl3 (Cr1-Cr4: L = 2,6-R1-4-R2-C6H2-NCH-C6H4-2-PPh2; Cr1: R1 = H, R2 = H; Cr2: R1 = Me, R2 = H; Cr3: R1 = iPr, R2 = H; Cr4: R1 = Ph2CH, R2 = iPr), have been synthesized and characterized by elemental analysis, ESI and IR spectroscopy. The molecular structures of Cr3 and Cr4 are defined by X-ray diffraction, revealing a distorted octahedral geometry around the chromium center in both structures. In the presence of an aluminum cocatalyst, complexes Cr1-Cr4 show moderate to high activities toward ethylene polymerization. The nature of the catalysts and various reaction conditions, such as the nature and the amount of cocatalyst, reaction time and temperature, are investigated in detail. The results show that the title complexes have good thermal stability and the substituents on the ligands significantly affect the catalytic properties. Particularly, complex Cr4 can produce HDPE with a high molecular weight up to 68.3 × 104 g mol-1 due to the suppression of the chain transfer/termination by the introduction of bulky Ph2CH groups.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

A new application about 2-(Diphenylphosphino)benzaldehyde

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A series of 2,6-dibenzhydryl substituted bulky Ni and Pd complexes containing P,N-chelating ligands, {[2,6-(Ph2CH)2-4-R-C6H2-N=CH-C6H4-2-PPh2]MX2; MX2 =NiBr2; R = Me (Ni1); R = F (Ni2); MX2 =PdCl2, R = Me (Pd1)}, have been prepared and used as catalyst precursors for ethylene oligo-/polymerization. Compared to the corresponding 2,6-diisopropyl Ni catalyst, these bulky Ni precatalysts activated by Et2AlCl exhibited excellent catalytic performance toward ethylene polymerization with activity of up to 1.90 × 105 g PE (mol Ni)?1 h?1, and result in semicrystalline PEs with high molecular weight. The catalytic performance of these bulky P,N-type complexes was significantly improved by introducing two ortho-dibenzhydryl on the N-aryl substituents. However, the formation of C10?C24 oligomers were generated using their palladium catalysts through ethylene oligomerization at high temperatures.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate