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 addition of trimethylphosphane to five-membered metallacyclic vinylketone complexes of the type ArR) (I) (Ar = η5-aromatic ring system: C5H5, C5H4Me, C5Me5; R = Me, Et, n-Bu; M = Mo, W) in pentane solution results in the formation of the ylidic metallacyclopropane complexes ArH(COR)] (II). In these 1:1 adducts the three-membered ring is stabilized by an electron-donating phosphonium and an electron-attracting acyl substituent. The negative charge in the ylidic complexes II is localized on the central metal providing it with Lewis base properties. An extraordinary high electron density can be observed on the metal of the derivative C5H5H-(COMe)] (III) which is formed by a 1:2 addition of C5H5W(CO)(C2H2)-(COMe) and PMe3. The metallacyclopropane complexes II and III are characterized by IR, 1H NMR, 13C NMR, 31P NMR and mass spectroscopy. For C5H5H(COMe)], the results of an X-ray structure determination are presented. 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
η5-C5H5(CO)2FeNa reacts with the benzimide chlorides C6H5(Cl)CNR (R CH(CH3)2, C6H5) in boiling THF to give the η1-iminoacyl complexes η5-C5H5 (CO)2Fe[η1-C(C6H5)NR]. Alternatively, the new Fe complexes [η5-C5H5(CO)FeCH3PF6 (IV) and [η5-C5H5(CO)2FeC(C6H5)N(CH3)C(C6H5)NCH3]PF6 (V) are formed under the same conditions, if R CH3. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η5-C5H5(CO)2FeC(C6H5)NHCH3]PF6 (VII). Reaction of η5-C5H5(CO)2 with N-benyzylbenzimido chloride yields η5-C5H5(CO)2FeCH2C6H5 as the only isolated product. 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 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 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
The amine substituted phosphines (C6H5)2PN(H)CH2CH3 and (C6H5)2PN(H)CH2C6H5 react with C5H5Fe(CO)2CH(C6H5) (OCH3) photolytically to give moderate yields of the four-membered chelate ring complexes C5H5H (C6H5)] and C5H5H(C6H5)], respectively. Photolysis of C5H5Fe(CO)2CH(C6H5) (OCH3) in the presence of (S)-(?)-diphenyl(1-phenylethylamino)phosphine leads to the isolation of C5H5Fe(CO)[(C6H5)2PNC(CH3) (C6H5)]CH2C6H5 which is proposed to arise from a formally 1,3-hydrogen shift rearrangement of an intermediate four-membered chelate ring complex. 相似文献
The six- and seven-membered rhenacycloalkanes (OC)4RH2 (R = CH3, CoH5; X = CH2, CH2CH2) are obtained by reaction of the binuclear anions [(OC)4RePR2O]22? with the alkanediylbis(triflouromethanesulfonates) X(CH2Y)2 (Y = CF3SO2O) in dimethoxyethane. In the Reσ bond of (OC)4RH2SO2 can be inserted under ring expansion. The rhenacycloheptanes (OC)4RH2 (R = CH3, CoH5) are thermally unstable and decompose by cleavage of the α-CC bond. The heterolytic cleavage of the ReRe bond in [(OC)4RePR2O]22? results in the open chain, ionic intermediate products [R2(O)PRe(CO)4CH2XCH2Y]?, which in competition with the cyclisation, are liable to a β-hydrogen transfer. The mechanisms which are responsible for the formation of the hdrido complexes [HRe(CO)4PR2O]? and HRe(CO)4PR2OCH2XCH3, are discussed. 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
The colourless, six- and seven-membered manganacycloalkanes (OC)4H2 are obtained by reaction of Na2[(OC)4MnPR2O] with the bis(triflate)alkanes (YCH2)2X (R = C6H5; X = CH2, C(CH3)2, CH2CH2; Y = CF3SO3). CO or SO2 can be inserted into the reactive MnC-σ bonds under ring expansion. Some characteristic IR and 1H NMR data are discussed. (OC)4H2 crystallizes monoclinic in the space group P21/c with Z = 4. 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
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 kinetics of the reaction of arylcyclopropanes (4-XC6H4C3H5, X = H, Me, EtO) with either [Pt2Cl2(μ-Cl)2(C2H4)2] or [{H2)} in tetrahydrofuran to give in each case [{H2)}4] and ethylene or cyclopropane, respectively, have been studied. The reactions are essentially first order in both arylcyclopropane and platinum complexes. The order of reactivity follows the series X = EtO > > Me > H, and [Pt2Cl2(μ-Cl)2(C2H4)2]> [{H2)}4] and the rate is accelerated in polar solvents. Mechanisms in which the arylcyclopropane first coordinates to platinum and then undergoes ring opening reactions are proposed. 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
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 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
