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Phosphane Complexes (phosphane + complex)
Selected AbstractsSynthesis, Structural Characterisation and Reactions of Some Vinylgold(I) Phosphane ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2006Fabian Mohr Abstract A series of vinylgold(I) complexes [Au(CR=CHR)L] (R = H, Me; L = PPh3, PPh2Me, PPhMe2) were prepared from the reaction of the Grignard reagents [MgBr(CR=CHR)] (R = H, Me) with the gold(I) phosphane complexes [AuCl(L)] (L = PPh3, PPh2Me, PPhMe2) at low temperature. The complexes were characterised by various spectroscopic techniques and, in the case of [Au(CMe=CHMe)(PPh3)], by a single-crystal X-ray structure determination. The gold,carbon bonds of these vinylgold(I) complexes are easily cleaved by acids and, in the presence of potassium permanganate, by species containing acidic protons. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Dramatic Pressure Effects on the Selectivity of the Aqueous/Organic Biphasic Hydrogenation of trans -Cinnamaldehyde Catalyzed by Water-Soluble Ru(II)-Tertiary Phosphane ComplexesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2003Gábor Papp Abstract In a water/chlorobenzene biphasic reaction, the hydrogenation of trans- cinnamaldehyde, catalyzed by water-soluble Ru(II)-phosphane complexes at pH,3.04 (phosphate buffer), produces a 61:39 mixture of cinnamyl alcohol and dihydrocinnamaldehyde at 1,bar H2; however, the selectivity is increased to 93:7 by increasing the hydrogen pressure to 8,bar. [source] Synthesis, Coordination and Catalytic Utility of Novel Phosphanyl,ferrocenecarboxylic Ligands Combining Planar and Central ChiralityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2007Martin Lama Abstract The chiral ferrocene derivative (R,Rp)-2-[1-(diphenylphosphanyl)ethyl]ferrocenecarboxylic acid (1) is prepared together with selected derivatives resulting from modification at the phosphane moiety [P -oxide (5) and P -sulfide (4)] and the carboxyl group {amides bearing benzyl (6) and (R)- or (S)-1-phenylethyl substituents [(R)- 7 and (S)- 7] at the amide nitrogen atom}. Acid 1 and amide 6 are studied as ligands in rhodium and palladium complexes. Bridge cleavage of the dimer [{Rh(,-Cl)Cl(,5 -C5Me5)}2] with 1 gives [RhCl2(,5 -C5Me5)(1 -,P)] (9) containing P-monodentate 1, which undergoes smooth conversion to the (phosphanylalkyl)ferrocenecarboxylato complex [RhCl(,5 -C5Me5){Fe(,5 -C5H5)(,5 -C5H3 -1-CH(Me)PPh2 -2-COO-,2O,P}] (10) upon treatment with silica gel or alumina. Yet another O,P -chelate complex,[Rh{Fe(,5 -C5H5)(,5 -C5H3 -1-CH(Me)PPh2 -2-COO-,2O,P}(CO)(PCy3)] (11; Cy = cyclohexyl) is obtained directly by an acid-base reaction between the acetylacetonato complex [Rh(acac)(CO)(PCy3)] and 1. Amide 6 reacts with [{Pd(,-Cl)(,3 -C3H5)}2] to give the expected phosphane complex [PdCl(,3 -C3H5)(6 -,P)] (12), while the replacement of the cyclooctadiene (cod) ligand in [PdCl(Me)(cod)] affords the chelate complex [PdCl(Me)(6 -,2O,P)] (13). All compounds are characterised by spectroscopic methods and the solid-state structures of 5, 9, 11, 13, (R,Sp)-2-[1-(diphenylphosphoryl)ethyl]-1-[N -(R)-(1-phenylethyl)carbamoyl]ferrocene [(R)- 8; phosphane oxide from (R)- 7], and the synthetic precursors (R,Sp)-1-bromo-2-[1-(diphenylphosphanyl)ethyl]ferrocene (2) and (R,Sp)-1-bromo-2-[1-(diphenylthiophosphoryl)ethyl]ferrocene (3) determined by single-crystal X-ray diffraction. The catalytic properties of 1 and the amides are probed in enanatioselective rhodium-catalysed hydrogenation and palladium-catalysed asymmetric allylic alkylation. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] [Tris(pyrazolyl)methane]ruthenium Complexes Capable of Inhibiting Cancer Cell GrowthEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 31 2009Jesse M. Walker Abstract The [tris(pyrazolyl)methane]ruthenium complexes [(,3 -tpm)RuCl(solv)2]PF6 [tpm = tris(pyrazolyl)methane; solv = MeCN, dmso] and [(,3 -tpm)RuCl(LL)]PF6 [LL = ,2 -dppe, ,2 -dppp, ,2 -dppb, (PMePh2)2] have been prepared, characterized and screened in vitro for their antiproliferative properties against the MCF-7 (breast) and HeLa (cervical) cancer cell lines by using the MTT assay. Although the MeCN and dmso complexes showed no activity under the conditions used, the phosphane complexes exhibited remarkable cytotoxic behaviour. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Strong Evidence for an Unprecedented Borderline Case of Dissociation and Cycloaddition in Open-Shell 1,3-Dipole Chemistry: Transient Nitrilium Phosphane-Ylide Complex Radical CationsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2009Holger Helten Abstract The reaction of 3-ferrocenyl-substituted 2H -azaphosphirene complexes 1a,c in the presence of substoichiometric amounts of ferrocenium hexafluorophosphate yields 3,5-diferrocenyl-substituted 2H -1,4,2-diazaphosphole complexes 3a,c and difluoro(organo)phosphane complexes 4a,c. The reaction of 1a,c and [FcH]PF6 with cyanoferrocene yields 3a,c in a straightforward way. The molecular structures of 3a,c were unambiguously identified by multinuclear NMR spectroscopic experiments, mass spectrometry, and single-crystal X-ray diffraction studies. DFT calculations on model complexes 1d,m and 3d,m reveal a close similarity of Mo and W complexes (vs. Cr) and a strong influence of the ferrocenyl substituent on the geometry, spin, and charge distribution of reactive intermediates and the reaction course. Strong support for the assumption of a dissociation,cycloaddition reaction sequence leading to 3 and thus a surprising "cannibalistic" reaction was obtained.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Luminescent Gold(I) and Copper(I) Phosphane Complexes Containing the 4-Nitrophenylthiolate Ligand: Observation of ,,,* Charge-Transfer EmissionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2008Cheng-Hui Li Abstract Gold(I) and copper(I) phosphane complexes containing the 4-nitrophenylthiolate ligand, namely [(PCy3)Au(SC6H4NO2 -4)] (1) (PCy3 = tricyclohexylphosphane), [Au2(,-dcpm)(SC6H4NO2 -4)2] (2) [dcpm = bis(dicyclohexylphosphanyl)methane], [Au2(,-dppm)(SC6H4NO2 -4)2] (3) [dppm = bis(diphenylphosphanyl)methane], and [(,2 -SC6H4NO2 -4)2(,3 -SC6H4NO2 -4)2(CuPPh3)4] (4), were prepared and characterized by X-ray crystal analysis. All of these complexes show an intense absorption band with ,max at 396,409 nm attributed to the intraligand (IL) ,(S),,*(C6H4NO2 -4) charge-transfer transition. The assignment is supported by the results of DFT and TDDFT calculations on the model complexes [PH3Au(SC6H4NO2 -4)] and [(,2 -SC6H4NO2 -4)2(,3 -SC6H4NO2 -4)2(CuPH3)4]. The emissions of solid samples and glassy solutions (methanol/ethanol, 1:4, v/v) of 1,4 at 77 K are assigned to the [,(S),,*(C6H4NO2 -4)] charge-transfer excited state. Metallophilic interactions are not observed in both solid state and solutions of complexes 1,3. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis, Structural Characterisation and Reactions of Some Vinylgold(I) Phosphane ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2006Fabian Mohr Abstract A series of vinylgold(I) complexes [Au(CR=CHR)L] (R = H, Me; L = PPh3, PPh2Me, PPhMe2) were prepared from the reaction of the Grignard reagents [MgBr(CR=CHR)] (R = H, Me) with the gold(I) phosphane complexes [AuCl(L)] (L = PPh3, PPh2Me, PPhMe2) at low temperature. The complexes were characterised by various spectroscopic techniques and, in the case of [Au(CMe=CHMe)(PPh3)], by a single-crystal X-ray structure determination. The gold,carbon bonds of these vinylgold(I) complexes are easily cleaved by acids and, in the presence of potassium permanganate, by species containing acidic protons. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] The Synthesis and Characterisation of Bis(phosphane)-Linked (6 - p -Cymene)ruthenium(II),Borane CompoundsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2005Adrian B. Chaplin Abstract The reaction of [(,6 - p -cymene)RuCl2]2 with some bis(phosphane) ligands (dppm, dppe, dppv, dppa, dpp14b, dppf) has been investigated. In general mixtures of products were obtained, although the pendant phosphane complexes [(,6 - p -cymene)RuCl2(,1 -dppv)] and [(,6 - p -cymene)RuCl2(,1 -dppa)] were isolated and characterized in the solid state by X-ray diffraction. The later complex was obtained in lower yield and undergoes an equilibration reaction resulting in the formation of a dimeric species, where the dppa bridges two ruthenium centres, and uncoordinated phosphane; the bridging species was also structurally characterised in the solid state. In contrast, the reaction of [(,6 - p -cymene)RuCl2(PPh3)] with dppa in the presence of [NH4]PF6 results in the formation of [(,6 - p -cymene)RuCl(PPh3)(,1 -dppa)]PF6, which is stable in solution. A series of linked ruthenium,borane complexes, viz. [(,6 - p -cymene)RuCl2(,1 -phosphane-BH3)] (phosphane = dppm, dppe, dppv, dppa, dpp14b, dppf) and [(,6 - p -cymene)RuCl(PPh3)(,1 -dppa-BH3)]PF6 have been prepared from isolated pendant phosphane complexes, those generated in situ, or from a preformed phosphane,borane adduct. The solid-state structures of [(,6 - p -cymene)RuCl2(,1 -dppm-BH3)], [(,6 - p -cymene)RuCl2(,1 -dppe-BH3)] and [(,6 - p -cymene)RuCl2(,1 -dppv-BH3)] have been determined by X-ray diffraction analysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Scope and Limitations of Palladium-Catalyzed Cross-Coupling Reactions with Organogold CompoundsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 8 2010A. Stephen Abstract Five different alkenylgold(I) phosphane complexes were prepared and then investigated in [1,1,-bis(diphenylphosphino)ferrocene]palladium(II) dichloride-catalyzed cross-coupling reactions with different aryl halides, heterocyclic halides, an alkenyl halide, an alkynyl halide, allylic substrates, benzyl bromide and an acid chloride. With regard to the halides, the iodides were highly reactive, bromides or chlorides gave significantly reduced yields or failed, allylic acetates failed, too. The cross-coupling partners contained a number of different functional groups, while free carboxylic acids did not deliver cross-coupling products and o,o -disubstituted arenes failed as well, a broad range of other functional groups like nitro groups, nitrile groups, ester groups, ,,,-unsaturated ester groups and lactones, aldehydes, alkoxy groups, pyridyl groups, thienyl groups, unprotected phenols and anilines, even aryl azides were tolerated. The structures of one alkenylgold(I) species and of four of the cross-coupling products were proved by crystal structure analyses. [source] Dramatic Pressure Effects on the Selectivity of the Aqueous/Organic Biphasic Hydrogenation of trans -Cinnamaldehyde Catalyzed by Water-Soluble Ru(II)-Tertiary Phosphane ComplexesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2003Gábor Papp Abstract In a water/chlorobenzene biphasic reaction, the hydrogenation of trans- cinnamaldehyde, catalyzed by water-soluble Ru(II)-phosphane complexes at pH,3.04 (phosphate buffer), produces a 61:39 mixture of cinnamyl alcohol and dihydrocinnamaldehyde at 1,bar H2; however, the selectivity is increased to 93:7 by increasing the hydrogen pressure to 8,bar. [source] | ||||||||||