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 oxidation of [PtCl3(C2H4)]- by Cl2 in aqueous solution, to yield CH2ClCH2OH and [PtCl4]2-, has been shown to proceed through the following sequence of steps: [PtCl3(C2H4)] Cl2Cl [PtCl5(CH2CH2Cl)]2- [PtCl5(CH2CH2OH)]2- → [PtCl42- + CH2ClCH2OHEach of the steps and intermediates in this mechanistic sequence has been identified and characterized. 相似文献
The platinacyclobutane complexes PtCl2L2(C3H5Me)], L pyridine, CD3CN, or tetrahydrofuran, exist as mixtures of isomers containing PH2 or P groups in rapid equilibrium. Decomposition occurs in some cases to give [PtCl2L(CH3CH2CHCH2)]. Stereospecific skeletal isomerisation also occurs in metallocyclobutanes containing the groups PH2 PHR, when R aryl further decomposition gives ν-allylplatinum complexes. 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
Reaction of [PdCl2(PBut2Ph)]2 with silver acetate gives the internally metalated complex [PButPh]2(μ-Cl)2. This reacts with TlC5H5 and LiC5Me5 with chloride-bridge cleavage to yield C5R5PPButPh (R = H, Me). The complex [PBut2]2(μ-Cl)2,prepared from [PdCl2(PBut3)]2 and CH3COOAg, is analogously converted into C5R5But2. The chloride complex C5H5Pd(PBut5Ph)CI does not eliminate HCl to form C5H5PButPh. 相似文献
The interaction of azobenzene and MnR(CO)5 (R Me, Et, CH2Ph, CH2-C6Me5, COCF3, COCH2C6F5, COCH2OPh, Ph or C6F5) affords MPh)-(CO)4, together with a binuclear complex Mn2(CO)6(C12H10N2) in some cases. The metallation reaction is shown to proceed most readily with Mn-(CH2Ph)(CO)5; with this reagent, the metallated complexes MMe2)-(CO)3[PMe2(CH2Ph)] (two isomers) and MsMe2(CO)4 have been obtained on treatment with EMe2(CH2Ph) (E P and As, respectively). 相似文献
Treatment of [{Ir(COD)(μ-Cl)}2] with excess of the electron-rich olefin [Ar]2 (abbreviated as (LAr)2, Ar = C6H4Me-p or C6H4OMe-p) affords the ortho-metallated tricycle [)3], which for Ar = C6H4Me-p (Ia) with HCL yields [)2(LAr)]Cl (IV); X-ray data show that in IV there is an unexpectedly close Ir?C(o-aryl) contact (2;52(1) Å) involving the “free” LAr which compares with an IrC(o-aryl) distance of 2.09(3) Å in Ia or 2.07(3) Å in the ortho-metallated LAr ligand of complex IV. 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
In the 1H NMR spectrum of the complex [Os3H3(CO)9CH2]+ at 30°C, under conditions of rapid exchange, the single hydride resonance has two sets of satellites of equal intensity (separated by 32.0 and 28.8 Hz) caused by 187Os1H spin—spin coupling. The spectral data rule out the upright carbenium ion structure for the complex, and are consistent with the fluxional process involving hydrocarbon ligand rotation about the CH2 axis in a tilted structure, with concomitant rotation of the Os3H3(CO)9 moiety. 相似文献
Variable temperature 1H NMR spectroscopy has been used in the study of 1,3-intramolecular shifts of the M(CO)5 moiety in complexes of the general formula [M(CO)5L], (M = Cr or w), L = H2, H2 and H2. For the 1,3,5-trithian complexes precise energy barriers for the process have been obtained by detailed computer simulation of the static and dynamic spectra. Our results suggest that the magnitude of ΔG≠ (298.15 K) for the 1,3-shift is largely dependent upon the skeletal flexibility of the ligand system. In this context we have investigated the X-ray crystal structure of the highly substituted trithian complex [W(CO)5{β-H(Me)}]. 相似文献
The photolysis of [I2H2 (PMe2 Ph)2] gives ethylene and but-1-ene as volatile products, the latter probably being formed via a five-coordinate platinum intermediate. However, the formation of propene from the photolysis of [Cl2H2 (1,10-phenanthroline) appears to involve a direct transfer of a hydrogen atom between neighbouring CH2 groups in the ring. Other gaseous products, e.g. cyclopropane, ethylene, may be formed via a platinum ion radical. 相似文献
The products of the photolysis of a number of platinacyclopentanes in solution at 25°C under a variety of conditions have been determined. With [I2PH2(L2)] (L = PMe2Ph, PPh3) in CH2Cl2, CH2Br2 and (CH3)2SO the hydrocarbon products are exclusively ethylene and but-1-ene. Formation of the latter through a 1,3-hydrogen shift is preceded by phosphine ligand dissociation. The photolysis of [ICH3PH2(L2)] gave methane, ethylene, but-1-ene and n-pentane together with a little n-butane, the methane being formed from internal hydrogen abstraction by the CH3 group in the excited reactant molecule. Photodecomposition of the platinum(II) compounds [PH2(L2)] (L = (PMe2Ph)2, (PPh3)2, Ph2PCH2CH2PPh2) gave ethylene, but-1-ene, pent-1-ene (with the halogenated solvents) and with some systems appreciable yields of n-butane, the latter being the results of internal abstraction of two hydrogen atoms by the C4H8 moiety. The formation of pentene is probably preceeded by the addition of CH2Cl2 or CH2Br2 to the excited reactant molecule. Addition of diphenylphosphine promotes the production of n-butane. 相似文献
A number of carbene complexes of formulas Cl3GeMn(CO)4C(OR′)R and C5H5Mo(CO)2(GeCl3)C(OR′)CH3 (R = CH3, C6H5; R′ = CH3, C2H5) have been prepared by the reaction of [N(C2H5)4]GeCl3 with CH3Mn(CO)5, C6H5Mn(CO)5, or C5H5Mo(CO)3CH3 followed by alkylation of the resulting trichlorogermylacylcarbonylmetallate ion. The compound C5H5Mo(CO)2(GeCl3)H2 has been prepared directly by the reaction of [N(C2H5)4]GeCl3 with C5H5Mo(CO)3(CH2)3Br. 相似文献
Reaction of R—N=CH—CH=N—R with [(CH3)3Al]2 affords the coordination product (CH3)3AlRN=CH—CH=NR (A) for R = 2,6-(CH3)2C6H3 and 2,4,6(CH3)3C6H2. For R = 4 ClC6H4, 4-CH3C6H4 and 4-CH3OC6H4, insertion takes place, giving the complexes (CH3)2A—R (B), in which Al is part of a five-membered chelate ring. Depending on the temperature both the addition and insertion products rearrange intramolecularly to the complexes (CH3)2-A—R (C), in which Al is also part of a five-membered chelate ring. Reactions of the asymmetric (CH3)2HC—N=CH—C(CH3)=N—CH-(CH3)2 with [Al(CH3)3]2 also leads to an insertion product, (CH3)2A—R (B') (R = (CH3)2CH), but there is no subsequent rearrangement in this case.A mechanism involving hydrogen migration is tentatively proposed to account for the observed isomerization, which increases in rate in the order:R = (CH3)3C>2,4,6-(CH3)3C6H2> 2,6-(CH3)2C6H3 (A → C)andR = 4-CH3OC6H4>4-CH3C6H4>4-ClC6H4 (B → C)Hydrolysis of isomer C gives the unknown imino amines R—NH—CH2-C(CH3)=N—R in quantitative yield. 相似文献
Treatment of Ir2Cl2(C8H14)4 with the phosphines t-Bu3?nP(CH2CMe3)n (n = 3,2,1) in hot toluene followed by crystallization of the products from C7H8/ EtOH mixtures gave the cyclometallated hydrides (C8H14)2Ir-μ-Cl2(CH2CMe3)2][P(CH2 (I) [t-BuP(CH2CMe3)2]2H2Ir-μ-Cl2But(CH2CMe3)][t-BuP(CH2CMe3)2] (II), and [(t-Bu2rCl]2 (III). The dihydrides IrH2Cl[t-BuP(CH2CMe3)2]2 (IIa) and IrH2Cl(t-Bu2PCH2CMe3)2 (IIIa) were also isolated; these species were, however, more conveniently obtained by bubbling hydrogen through the solution of Ir2Cl2 (C8H14)4 and the respective phosphine in toluene. i-Pr3 reacted with the olefiniridium(I) precursor in C7H8/EtOH to yield the carbonyl complexes (i-Pr3P)2H2Ir-μ-Cl2Ir(CO)(PPri3)2 (IV) and IrCl(CO)(PPi3)2 (IVa), no cyclometallated product being detected. The stereochemistries of the complexes were deduced from IR, 1H, 31P, and 13C NMR data. The crystal structures of IIIa and IVa were also determined. 相似文献
Silicon-transition metallic silacyclobutanes CpFe(L2)H2 [L = CO or Ph2MeP; or L2 = (CO)(Ph2MeP)] have been prepared and their reactions (substitution at Si or Fe, Si—Fe cleavage, or ring-opening) studied. 相似文献
C5H5FeC5H4CH2NMe2 reacts with sodium chloropalladate(II) in the presence of sodium acetate to give the internally metallated binuclear species [Me2}2] (X = Cl). The corresponding iodide was prepared as were mononuclear species [Me2}] and [Me2}L] L = PMe2Ph, AsMe2Ph, P(OMe)3 or PPh3. 1H NMR data are given. 相似文献
When (t-Bu)2PCH2CHCH2CH2 is combined with [IrCl(C8H14)2]2 in toluene, the σ-bound cyclopropane complexes (P(t-Bu)2CH2H2) (1a, 1b) are formed. Complexes 1a,1b react readily with H2 to form IrClH2P(t-Bu)2CH2H2)2 (2). In polar solvents 1a,1b isomerize to the σ-vinyl chelated complex H)(P(t-Bu)2CH2H2) (3). The structure of this 5-coordinate, 16-electron IrIII complex was deduced from spectroscopic data, reaction chemistry, and from the crystal structure of its CO adduct (4). Compound 4 crystallizes in the monoclinic space group C2h5-P21/n (a 15.610(14), b 15.763(16), c 11.973(13) Å, and β 104.74(5)°) with 4 molecules per unit cell. The final agreement indices for 2326 reflections having Fo2 > 3σ(Fo2) are R(F) = 0.089 and Rw(F) = 0.095 (271 variables) while R(F2) is 0.148 for the 3423 unique data. Bond lengths in the 5-atom chelate ring are IrP 2.341(4), PC 1.857(26), CC 1.520(30), CC 1.341(25), and CIr 1.994(21) Å. The IrCl distance is 2.479(5) Å. 相似文献
The platinacyclopentane derivative [Cl(CH2)3R2P](Cl) is formed by action of Cl(CH2)3PR2 on Pt(COD)2 in n-hexane via the not isolable Pt[PR2(CH2)3Cl]2 (R C6H11) by oxidative addition of a CCl bond to platinum. [μ-CIRh(CO)2]2 reacts in benzene with Cl(CH2)3PR2 under partially CO substitution to give the stable intermediate Cl(OC)Rh[PR2(CH2)3Cl]2. In boiling toluene oxidative addition of a CCl bond to rhodium occurs under formation of the phospharhodacyclopentane [CI(CH2)3R2P] Cl2(OC)- (R C6H5). The 31P{1H}-NMR spectra of the rhodium compound is characterized by an ABX system, that of the platinum by superposition of an ABX pattern with an AB spectrum. 相似文献
Complexes of the types (C5H5)2TiClL, (C5H5)TiClL2 and [(C5H4)TiL2]2 (L is a monofunctional bidentate ligand) have been made by reactions of titanocene dichioride with the substituted pyrazolones, RCOCH3 (where R = CH3, C2H6, C6H5 and p-ClC6H4) in the presence of triethylamine in refluxing THF. A possible mechanism for the formation of [(C5H4)TiL2]2 is suggested. 相似文献
