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1.
The five polyhalides [(Ph)(3)PBr][Br(7)], [(Bz)(Ph)(3)P](2)[Br(8)], [(n-Bu)(3)MeN](2)[Br(20)], [C(4)MPyr](2)[Br(20)] ([C(4)MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)(3)PCl](2)[Cl(2)I(14)] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)(3)PBr][Br(7)] and [(Bz)(Ph)(3)P](2)[Br(8)] contain discrete pyramidal [Br(7)](-) and Z-shaped [Br(8)](2-) polybromide anions. [(n-Bu)(3)MeN](2)[Br(20)] and [C(4)MPyr](2)[Br(20)] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)(3)PCl](2)[Cl(2)I(14)] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br(2) and ICl and that, on the other hand, reduces the high volatility of the molecular halogens. 相似文献
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Syntheses and Crystal Structures of [(Ph3As)2CCN–MnBr3], [(Ph3As)2CCN–CoBr3], and [(Ph3As)2CCN]+CuBr2– The di(arsa)acetonitrilium bromide [(Ph3As)2CCN]Br reacts with the anhydrous dibromides of manganese and cobalt in acetonitrile to form the molecular complexes [(Ph3As)2CCN–MBr3] [M = ( 1 ), Co( 2 )] with zwitterionic structures. With copper(I)bromide, however, the ionic compound [(Ph3As)2CCN]+CuBr2– ( 3 ) is formed. All complexes are characterized by IR spectroscopy and by crystal structure analyses. 1 and 2 crystallize isotypically with each other in the space group P 1 with two formula units per unit cell. The MBr3– fragments in the molecular complexes are connected to the N atom of the [(Ph3As)2CCN]+ cation showing bond angles C–N–Mn of 156.9° and C–N–Co of 161°, and distances Mn–N of 215.6 pm and Co–N of 201 pm. In 3 , on the other hand, (space group C2/c, Z = 4) the ions [(Ph3As)2CCN]+ and the linear Br–Cu–Br– ion are to be found concurrent but separate. 相似文献
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The interaction of cis-[(Ph3PCH2)(Ph3P)PtCl2] with aluminium(III) chloride in CH2Cl2 affords the three coordinate cationic platinum(II) complex [(Ph3PCH2)(Ph3P)PtCl][AlCl4] which is a useful starting material for platinum complexes with four different ligands. With Ph3As and Me2S the cationic phosphorus ylide complexes [(Ph3PCH2)(Ph3P)(Ph3As)PtCl][AlCl4] and [(Ph3PCH2)(Ph3P)(Me2S)PtCl][AlCl4] are formed. 851 V 3 相似文献
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Facile and highly selective perfluoroalkyl-aryl reductive elimination from a metal center (Pd) has been demonstrated for the first time. At temperatures as low as 50-80 degrees C, [(Xantphos)Pd(Ph)CF3] undergoes remarkably clean decomposition to produce CF3Ph in high yield and selectivity. In contrast, analogous trifluoromethylpalladium aryls stabilized by rigid cis-chelating ligands such as dppe are completely unreactive at temperatures up to 130-140 degrees C. Decomposition of [(Ph3P)2Pd(Ph)CF3] in the presence of PhI in benzene at 60 degrees C does not produce PhCF3 but rather leads to [(Ph3P)2Pd(Ph)I] and [Ph4P]+[(Ph3P)Pd(CF3)3]- in a 2:1 ratio with high selectivity. 相似文献
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《Journal of Molecular Catalysis #》1984,22(3):341-348
In addition to known catalytic dehydrogenations, the o-phenylene- diamine (OPD)/cobalt(II) system also effects the oxidation of PH3P to Ph3PO. A green intermediate of the formula [Ph3P(OPD)2Co-O2-Co(OPD)2- Ph3P]4+ has been isolated and characterized. It is formed by the rapid co- ordination of Ph3P to cobalt(III) in the μ-peroxo precursor [(OPD)2Co—O2—Co(OPD)2]4+. The relative contribution of OPD dehydrogenation under catalytic conditions depends on the OPD to Ph3P ratio. Dioxygen is ultimately converted to water and no H2O2 is formed. The proposed mechanistic path involves concerted or stepwise O-atom transfer by species mimicking biological ‘oxenoid’ reagents. 相似文献
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Jim Bashkin Clive E. Briant D. Michael P. Mingos Robert W. M. Wardle 《Transition Metal Chemistry》1985,10(3):113-114
Summary [(Ph3P)AuCo(CO)3(PPh3)] has been synthesised from [(Ph3P)AuCo(CO)4], PPh3v and Me3NO in acetonitrile. Its molecular structure, determined by single-crystal x-ray crystallography, consists of an almost linear
P-Au-Co-P arrangement in which the Co atom is in a slightly distorted trigonalbipyramidal geometry, with the Au and P atoms
occupying the apical sites. The Au-Co bond length of 2.450(1) ? is shorter than that reported for [(Ph3P)AuCo(CO)4]. The carbonyl ligands are bent towards the Au atom and the mean Au-Co-C angle is 81(1)°. 相似文献
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Song Y Butler IS Shaver A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(12):2581-2587
Infrared and FT-Raman spectra of cis-dimercaptobis(triphenylphosphine)platinum(II), cis-[(PPh3)2Pt(SH)2], have been measured at high external pressures up to 55 kbar with the aid of a diamond-anvil cell (DAC). The wavenumber (v) versus pressure (P) plots from the Raman data indicate the occurrence of a pressure-induced phase transition at around 15 kbar. The metal-ligand stretching mode, v(Pt-S), and the C-H stretching mode of the phenyl rings, v(C-H), are highly sensitive to the application of pressure (dv/dP approximately 1.0 cm(-1) kbar(-1)). The IR results are generally consistent with the Raman data. The pressure-induced phase transition is most probably attributable to the reorientation of the phenyl rings in the complex; similar results have been obtained for other phenyl derivatives. 相似文献
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Eduard Bernhardt David J. Brauer Martin Köckerling Prof. Dr. Gottfried Pawelke Dr. 《无机化学与普通化学杂志》2007,633(7):947-954
Trimethylamine‐tris(pentafluoroethyl)borane [(C2F5)3BNMe3] ( 1 ) reacts at 190 °C with water under displacement of the trimethylamine ligand to yield the hydroxy‐tris(pentafluoroethyl)borate [(C2F5)3BOH]? ( 2 ). In tributylamine 1 reacts with alkynes HC≡CR to form novel ethynyl‐tris(pentafluoroethyl)borate anions [(C2F5)3BC≡CR]? – R = C6H5 ( 3 ), C6H4CH3 ( 4 ), Si(CH(CH3)2)3 ( 5 ) – in moderate yields. Compound 3 adds water across the triple bond to form the novel anion [(C2F5)3BCH2(CO)C6H5]? ( 6 ). The structures of [(C2F5)3BNMe3], [NMe4][(C2F5)3BOH] and K[(C2F5)3BCH2(CO)C6H5] have been determined by x‐ray crystallography. 相似文献
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Dawid J. Babula Rex S. C. Charman Thomas H. Jerome Dr. Thomas M. Horsley Downie Dr. Mary F. Mahon Dr. David J. Liptrot 《欧洲无机化学杂志》2023,26(13):e202300043
σ-Bond metathesis reactions between [(6-Dipp)CuOtBu] (6-Dipp=:C({Dipp}NCH2)2CH2, Dipp=2,6-iPr2−C6H3) and three diboranes gave access to three new copper(I) boryl complexes [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex] (cat=1,2-O2C6H4; neop=(OCH2)2C(CH3)2; hex=OC(CH3)HCH2C(CH3)2O). Whilst [(6-Dipp)CuBcat] and [(6-Dipp)CuBneop] formed rapidly in toluene, access to [(6-Dipp)CuBhex] required heating to 60 °C for days. The complexes were characterised by single-crystal X-ray crystallography which showed in all three cases that the systems were monomers and distorted-linear at the copper atom. The stability of [(6-Dipp)CuBneop] was found to be comparable to that of [(IPr*)Cu-Bneop] (IPr*=1,3-bis(2,6-(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene); it persisted in solution for days with no sign of decomposition. [(6-Dipp)CuBhex] is a rare crystallographically characterised example of a complex containing a boryl anion supported by the hexylene glycolato ligand. 相似文献
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Monodispersed Ag2Se nanocubes and faceted nanocrystals have been synthesized by hexadecylamine (HDA) induced thermolysis of [(PPh3)3Ag2(SeC{O}Ph)2] in a mixture of TOP (tri-n-octyl phosphine) and HDA in the temperature range 95-180 degrees C. 相似文献
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Haiying Zhang Jiarou Peng Shiqi Peng Guowang Wu Duenhua Dai Guozheng Zhu 《Journal of mass spectrometry : JMS》1992,27(1):50-52
The reactions of sulphur with phosphine and phosphite were investigated by low-energy electron impact mass spectrometry and fast atom bombardment mass spectrometry. A previously reported mechanism of the Ph3P–S8 reaction was supported and a possible mechanism for the (PhO)3P–S8 reaction is proposed. 相似文献
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Erhardt S Grushin VV Kilpatrick AH Macgregor SA Marshall WJ Roe DC 《Journal of the American Chemical Society》2008,130(14):4828-4845
Reaction paths leading to palladium catalyst deactivation during cyanation of haloarenes (eq 1) have been identified and studied. Each key step of the catalytic loop (Scheme 1) can be disrupted by excess cyanide, including ArX oxidative addition, X/CN exchange, and ArCN reductive elimination. The catalytic reaction is terminated via the facile formation of inactive [(CN)4Pd]2-, [(CN)3PdH]2-, and [(CN)3PdAr]2-. Moisture is particularly harmful to the catalysis because of facile CN- hydrolysis to HCN that is highly reactive toward Pd(0). Depending on conditions, the reaction of [(Ph3P)4Pd] with HCN in the presence of extra CN- can give rise to [(CN)4Pd]2- and/or the remarkably stable new hydride [(CN)3PdH]2- (NMR, X-ray). The X/CN exchange and reductive elimination steps are vulnerable to excess CN- because of facile phosphine displacement leading to stable [(CN)3PdAr]2- that can undergo ArCN reductive elimination only in the absence of extra CN-. When a quaternary ammonium cation such as [Bu4N]+ is used as a phase-transfer agent for the cyanation reaction, C-N bond cleavage in the cation can occur via two different processes. In the presence of trace water, CN- hydrolysis yields HCN that reacts with Pd(0) to give [(CN)3PdH]2-. This also releases highly active OH- that causes Hofmann elimination of [Bu4N]+ to give Bu3N, 1-butene, and water. This decomposition mode is therefore catalytic in H2O. Under anhydrous conditions, the formation of a new species, [(CN)3PdBu]2-, is observed, and experimental studies suggest that electron-rich mixed cyano phosphine Pd(0) species are responsible for this unusual reaction. A combination of experimental (kinetics, labeling) and computational studies demonstrate that in this case C-N activation occurs via an S(N)2-type displacement of amine and rule out alternative 3-center C-N oxidative addition or Hofmann elimination processes. 相似文献
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Selective hydrogenation of carbon-carbon double bond in the presence of nitrogen-nitrogen double bond in (3-trifluoromethyl) phenyldiazirine achieved with Wilkinson's catalyst. 相似文献