3-Phenyl- and 3-p-bromophenyl-thiete 1,1-dioxides react with [Pt(trans-stilbene)(PPh3)2] and [Pt(AsPh3)4] to give the complexes [Pt(O2)(MPh3)2] (R Ph, p-BrC6H4; M P, As). 相似文献
Unstable transition metal compounds formed from hydridosilacyclobutanes are described: 1-methyl-1-silacyclobutane reacts with nonacarbonyldiiron to give the complexes [Fe(CO)4(H){H2}] and [(H)Me}(CO)4], and with bis(triphenylphosphine)(ethylene)platinum(0) to give [Pt(H)(PPh3)2{H2}]. 相似文献
The synthesis and properties of a series of trans-halocarbonylrhodium(I) complexes containing the phosphinoalkylorganosilicon ligands Me3SiCH2PPh2, Me3Si(CH2)3PPh2, and PPh2CH2(Me) have been investigated. The complexes could be prepared by an exchange reaction involving RhCl(CO)(PPh3)2 and the organosilicon ligands or in better yields by the reaction of Rh2Cl2(CO)4 with the ligands. Iodorhodium derivatives were obtained as the exclusive products in the latter reaction if a small amount of LiI was present. The catalytic activity of RhCl(CO)(PPh2CH2SiMe3)2 was similar to that of RhCl(CO)(PPh3)2 in the hydroformylation of hex-1-ene at 100°C and 1000 psi pressure of H2/CO. The catalytic properties of the iodo derivatives RhI(CO)L2 [L = Me3SiCH2PPh2, Me3Si(CH2)3PPh2, and PPh2CH2(Me)] varied considerably, with RhI(CO)(PPh2CH2SiMe3)2 producing an unexpectedly low linear/branched aldehyde product ratio. 相似文献
Amination of PtII-allene complexes of the type cis[PtCl2(Me2CCCHR)(PPh3)] gives the new four-membered C, N chelate aminoalkenyl complexes [Me2(PPh3)Cl]. These undergo ready insertion of carbon monoxide into the CPt σ-bond; the resulting acyl complexes are oxidized by hydrogen peroxide to aminoacidato complexes, and the free unsaturated β-aminoacids can be recovered in good yield by ligand displacement. 相似文献
The new phosphine, PBut2Bui (L), was prepared from But2PCl and LiBui. PPh2Bui (L′) was prepared from Ph2PCl and LiBui. Treatment of [PtCl2(NCBut)2] with L′ gives [PtCl2L′2] which does not cyclometallate even on prolonged boiling in 2-methoxyethanol. In contrast, [PtCl2(NCBut)2] reacts with PBut2Bui in boiling 2-methoxyethanol to give the cyclometallated complex [2)2] (II, X = Cl). The corresponding bromide, iodide and acetylacetonate were prepared. With PPh3 II (X = Cl) gives [2)(PPh3)] which with NaBH4 gives [H2)(PPh3)]. Na2PdCl4 with L (2 mol equivalents) gave trans-[PdCl2L2], which was converted into trans-[Pd(NCS)2-L2] by metathesis with KSCN. Treatment of Na2PdCl4 with L (1 mol equivalent) gave [Pd2Cl4L2], which on heating in 2-methoxyethanol gave [2)2], as a mixture of syn- and anti-isomers. The complexes trans-[PdCl2-L′2] and [Pd2Cl4L′2] were also prepared. 1H- and 31P NMR data are given. 相似文献
The osmium carbyne complex, Os(CR)Cl(CO)(PPh3)2, (R p-tolyl) reacts with Group I halides to form the mixed dimetallocyclopropene species, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, and [R)Cl(CO)(MeCN)(PPh3)2] ClO4 X-ray crystal structure determination of R)Cl(CO)(PPh3)2 confirms the presence of a three-membered ring and the structure can be viewed as the “acetylene-like” interaction of an osmium—carbon triple bond with AgCl. In acid solution AgCl is precipitated and an alkylidene complex results from proton addition to the carbyne ligand. 相似文献
Heating a toluene solution of dicarhomethoxyacetylenebis(triphenylphosphine)platinum(0) at 130°C gives the ortho-metalated complex (Ph3P)(Ph2t-trans-(COOMe)CCHCOOMe. 相似文献
Enthalpies, ΔH(1) ?94.8 ± 6.0 and ΔH(6) ?57.1 ± 5.1 kJ mol?1, of the following reactions have been measured calorimetrically [Pt(trans-stilbene)(PPh3)2](s) + dpcp(g) → (PPh3)2Pt(dpcb)(s) + trans-stilbene(g) (1) [Pt(trans-stilbene)(PPh3)2](s) + bcbd(g) → (PPh3)2Pt(bcpd)(s) + trans-stilbene (g) (6) where dpcp is diphenylcyclopropenone, (PPh3)2Pt(dpcb) is (1,1-bistriphenylphosphine)platinadiphenylcyclobutenone, (PPh3)2O, bcbd is benzocyclobutene-1,2-dione and (PPh3)2Pt(bcpd) is (1,1-bistriphenylphosphine)platinabenzocyclopentanedione, . It is concluded that the five-membered platinacyclo ring system in (PPh3)2Pt(dpcb) is not heavily strained. 相似文献
The reaction of [Pt((F3C)CCH(CF3))(P(C2H5)3)2CH3OH]PF6 with allene in methanol affords a novel metallocyclic ethereal complex [CH3)(P(C2H5)3)2]PF6, which has been characterized by 1H, 2H, 19F and 31P NMR spectroscopy. Its structure has also been determined by a single crystal X-ray analysis. The crystal are monoclinic, space group P21/n, with cell dimensions a 20.012(5), b 17.222(5), c 8.902(3) Å and β 91.54(5)°. The structure was refined by full matrix least-squares methods on F, using 3097 unique observations collected by automated four circle diffractometer. Refinement converged at R 0.066. The Pt atom has a distorted square-planar coordination geometry, with cis P atoms, and PtP distances of 2.219(4) Å (trans to O) and 2.324(4) Å (trans to C). These results show the ethereal group is a weak ligand to platinum(II) but because of the chelating effect, its displacement by other ligands is thermodynamically not favorable. The mechanism of formation of the ethereal complex is also discussed. 相似文献
The zerovalent carbyneosmium complex, OsCl(CC6H4NMe2)(CO)(PPh3)2, reacts with molecular oxygen giving a 1/1 adduct which is formulated as a divalent, octahedral complex retaining the unchanged carbyne ligand, and with a dihapto-peroxycarbonyl ligand, OO)Cl(CC6H4NMe2)(PPh3(2. Reaction with HCl liberates CO2 and forms [OsCl2(CC6H4NMe2)(H2O)(PPh3)2]+ from which have been derived, and structurally characterised by X-ray crystallography, the two octahedral complexes, OsCl2(NCS)(CC6H4NMe2)(PPh3)2 and [OsCl2(CC6H4NMe2)(CNR)(PPh3)2]+. The Os—carbyne distances in these two species are, respectively, 1.75(1) and 1.78(1) Å. 相似文献
The complexes trans-[PdCl{(ME)=NR'} (PPh3)2] (R=C6H11,p-C6H4OMe; R=p-C6H4OMe, Me) containing a σ-bonded 1,4-diaza-3-menthyl-butadiene-2-yl group with different substituents on the nitrogen atoms have been prepared by two routes. The first involves initial methylation of the mixed isonitrile complex [PdCl2(CNR)(CNR')]by HgMe2, followed by reaction with PPh3 (molar ratio ). The second method involves condensation of primary aliphatic amines with the carbonyl group of the 1-azabut-1-en-3-one-2-yl moiety of the complex trans-[PdCl{(Me) = 0} (PPh3)2]. The 1,4-diaza-3-methylbutadiene-2-yl derivatives act through their imino nitrogen atoms as chelating ligands towards anhydrous metal chlorides MCl2 (M = Co, Ni, Cu, Zn). Magnetic moment measurements and the far-infrared and electronic spectra of these adducts indicate an essentially pseudo-tetrahedral configuration at M in the solid and in solution. With the ZnCl2 adducts, the 1H NMR pattern for the phenyl protons of the p-methoxyphenyl N-substituents dependss upon the position of the substituent i the 1,4-diazabutadiene chain. 相似文献
The mixed dinitrogen-isocyanide complexes mer-[ReCl(N2)(CNMe)-{P(OMe)3}3] (I) and [ReCl(N2)(CNMe)(PPh3) {P(OEt)3}2] (II) are obtained by a novel route through reactions of CNMe with the organodiazenido species [ReCl2(NNCOPh) {P(OMe)3 }3] and [ReCl2(NNCOPh)(PPh3){P(OEt)3 }2] (III, newly synthesized), whereas mer-[ReCl(N2)(PPh3) {P(OMe)3 }3] (IV) (which gives I by reaction with CNMe) is formed in the reaction of [OPh)(PPh3)2] with P(OMe)3; the structure of complex I is authenticated by X-ray analysis. 相似文献
The series of cis/trans-trifluoromethylselenato complexes [Pt(SeCF3)2 − xClx(PPh3)2] (x = 0, 1) was identified by NMR spectroscopic methods. While in acetonitrile solution spectra are dominated by the resonances of the cis derivatives, those of pure cis-[Pt(SeCF3)2(PPh3)2] indicate cis-trans-isomerisation in CH2Cl2 solution. In contrast, exchange reactions of cis-[PtCl2(PPh3)2] and [NMe4]TeCF3 only gave evidence for cis isomers. Molecular structures of cis- and trans-[Pt(SeCF3)2(PPh3)2] and cis-[Pt(TeCF3)2(PPh3)2] are discussed in comparison with related compounds. 相似文献
The kinetics of the reaction of alkenes (e.g. cis-pent-2-ene, hex-1-ene, cyclopentene) with [H2)(THF)2] (X = Cl or Br, THF = tetrahydrofuran) or with [H2)(THF)2] in THF solution have been studied. The reactions occur with displacement of cyclopropane or phenylcyclopropane to give [PtCl2(olefin)(THF)], and follow essentially second order kinetics, first order in both platinum complex and olefin. The mechanism of reaction is discussed. 相似文献
The displacement of tetrahydrofuran (THF) from W(CO)5(THF) with hexaphenylcarbodiphosphorane yields a compound with a carbon-metal bond (CO)5W C[P(C6H5)3]2. The in situ photolysis of tungsten hexacarbonyl and hexaphenylcarbodiphosphorane, however, yields a product (CO)5W?CC +P(C6H5)3. Ethylenebis(triphenylphosphine)platinum and hexaphenylcarbodiphosphorane in benzene yield a platinum containing heterocycle [(C6H5)3P]2-(C6H5)3. 相似文献
The complex [Pt(C2H4)(PPh3)2] reacts with Pb2Ph6 to give cis-[PtPh(Pb2Ph5)(PPh3)2]; this decomposes in solution to cis-[PtPh(PbPh3)(PPh3)2], which may also be obtained from the ethylene complex and PbPh4. Lead compounds PbPhMe3 and PbPh3Br also give products of insertion into PbPh bonds, but PbMe3Cl gives cis- and trans-[PtCl(PbMe3)(PPh3)2]. The complex trans-[Pt(PbPh3)2(PEt3)2] reacts with 1,2-bis(diphenylphosphino)ethane (DPPE) to give [Pt(PbPh3)2(DPPE)] which readily decomposes in dichloromethane in presence of PEt3 to give [Pt(PbPh3)(PEt3)(DPPE)]Cl and [PtPh(PEt3)(DPPE)]Cl. The complex trans-[PtCl(PbPh3)(PEt3)2] was detected in the products of reactions between trans-[PtCl2(PEt3)2] and trans-[Pt(PbPh3)2(PEt3)2] or less than 2 moles of LiPbPh3; it was not detected in the mixture after treatment of trans -[Pt(PbPh3)2(PEt3)2] with HCl. In contrast to an earlier report, we were unable to detect lead-containing complexes in the products of the reaction between trans-[PtHCl(PPh3)2] and Ph3PbNO3. The complexes and their decomposition products were identified by pre31P-{1H} NMR spectroscopy. 相似文献
The electron deficient acetylene, hexafluorobut-2-yne, reacts with molybdenum and tungsten methanethiolate derivatives (prepared in situ) to give vinyl and three-, five-, or six-membered heterocyclic derivatives: [Cp(OC)- Me], [Cp(OC)2Me], [CpW(CO)3C(CF3C(CF3)SMe], [CpW{η3-(O)}-(CO)2]. These reactions contrast with those of trifluoropropyne where no organometallic species are obtained. On heating or irradiation with CF3CCCF3 [CpMH(CO)3] gives known bridged species and in the presence of dimethyl disulphide the vinyl derivative [CpM(CO)3C(CF3)C(CF3)H]and an isomer of undetermined structure. 相似文献
