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1.
The synthesis and properties of a series of trans-halocarbonylrhodium(I) complexes containing the phosphinoalkylorganosilicon ligands Me3SiCH2PPh2, Me3Si(CH2)3PPh2, and PPh2CH2(Me)Si(OSiMe2)3O 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)Si(OSiMe2)3O] varied considerably, with RhI(CO)(PPh2CH2SiMe3)2 producing an unexpectedly low linear/branched aldehyde product ratio.  相似文献   

2.
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, Os(O2CO)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   

3.
The cyclometallation of p-RC6H4CHNCH2C6H2, (R = H, Cl, NO2) by PdX2 (X = Cl, AcO) has been studied.In every case the cyclometallation occurs with formation of a five-membered ring containing the methine group. The structure of these compounds [PdX(p-RC6H3CHNCH2C6H5)]2, derived from 1H NMR spectra, are different from those reported previously. Reaction of these compounds with PEt3 gives the compounds [PdX(p-RC6H3CHNCH2C6H5)(PEt3)2] but with an excess of PPh3 only the complexes [PdX(p-RC6H3CHNCH2C6H5)(PPh3)] are formed.  相似文献   

4.
The addition of trimethylphosphane to five-membered metallacyclic vinylketone complexes of the type ArM(CO)2(HCCHCOR) (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 ArM(CO)2[(PMe3)-HCCH(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 C5H5W(CO)(PMe3)[(PMe3)HCCH-(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 C5H5W(CO)2[(PMe3)HCCH(COMe)], the results of an X-ray structure determination are presented.  相似文献   

5.
Os(η2-CH2O)(CO)2(PPh3)2 reacts with CSe2 to form a metallacycle Os(CH2OC[Se]Se)(CO)2(PPh3)2. This compound breaks down to Os(η2-CH2Se)(CO)2(PPh3)2 with probable loss of COSe. An alternative route to Os(η2-CH2Se)(CO)2(PPh3)2 and also Os(η2-CH2Te)(CO)2(PPh3)2 is through reaction of Os(CH2I)I(CO)2(PPh3)2 with SeH? and TeH?, respectively. HCl with Os(η2-CH2E)(CO)2(PPh3)2 (E = Se or Te) gives OsCl(EMe)(CO)2(PPh3)2 while methyl iodide gives [Os(η2-CH2EMe)(CO)2 - (PPh3)2] I. BH4? reacts with these cations to cleave the CE bond and form Os(CH3)(EMe)(CO)2(PPh3)2.  相似文献   

6.
Reactions of alloxan (all) with [PtL(PPh3)2] (L′= trans-stilbene, L″ diphenylacetylene) afford the side-bonded ketone complex [Pt(all)(PPh3)2] which may also be obtained from the hydrate of alloxan and [PtL′(Pph3)2]. Similarly diethyl oxomalonate (dio) and [Pt(PPh3)4] afford a side-bonded ketone complex [Pt(dio)(PPh3)2]. Reaction of isatin with [Pt(PPh34] gives trans-[PtH{NCO(o-C6H4)CO}(PPh3)2] and benzoyl cyanide and [PtL′(PPh3)2] give cis-[Pt(CN)(COPh3)2] and trans-[Pt(CN)2(PPh2)2].  相似文献   

7.
A reinvestigation of the reaction between C2(CO2Me)2 and RuH(PPh3)2(η-C5H5) and some related complexes is reported. Initial cis addition is followed by conversion into the trans isomer. In the case of the bis-(PPh3) complex, isomerisation is followed by chelation of the ester CO group with concomitant displacement of one PPh3ligand. The resulting chelate complex reacts with CO or CNBut to give the (Z)-RuC(CO2Me)CH(CO2Me) complexes; the (E)-isomer of the carbonyl complex is obtained by addition of C2(CO2Me)2to RuH(CO)(PPh3)(η-C5H5). The 1Hand 13C NMR spectra are not a reliable guide to assignment of the stereochemistry of the vinyl group. Other products isolated from the initial reaction are the bis-insertion product Ru{C(CO2Me)C(CO2Me)C(CO2Me)CH(CO2Me)} -(PPh3)(η-C5H5) and the 1/2 PPh3/C2(CO2Me)2 adduct. The molecular structures of Ru{(Z)-C(CO2Me)CH(CO2Me)}(CO)(PPh3(η-C5H5) · 0.5EtOH, Ru{(E)-C(C2Me)CH(CO2Me)}(dppe)(η-C5H5) and Ru{C(CO2Me)C(CO2Me)C(CO2-Me)CH(CO2Me)}(PPh3)(η-C5H5) have been determined. The cis isomer is monoclinic, space group P21,with a 9.328(8), b 17.385(10), c 10.356(7) Å, β 101.78(3)° and Z = 2; 2107 data with I ≥ 2.5σ(I) were refined to R = 0.076 Rw = 0.085. The trans isomer is triclinic, space group P1, with a 10.404(7) b 11.221(6), c 13.230(9) Å, α 92.67(5), β 110.56(5), γ 106.21(5)° and Z = 2; 2520 data with I ≥ 2.5σ(I) were refined to R = 0.055 Rw = 0.068. The butadienyl complex is monoclinic, space group P21/a, with a 19.655(8), b 8.674(4), c 21.060(5) Å, β 116.22(3)° and Z = 4; 2724 data with I ≥ 2.5σ(I) were refined to R = 0.042, Rw = 0.047.  相似文献   

8.
Unstable transition metal compounds formed from hydridosilacyclobutanes are described: 1-methyl-1-silacyclobutane reacts with nonacarbonyldiiron to give the complexes [Fe(CO)4(H){Si(Me)CH2CH2CH2}] and [Fe{CH2CH2CH2Si(H)Me}(CO)4], and with bis(triphenylphosphine)(ethylene)platinum(0) to give [Pt(H)(PPh3)2{Si(Me)CH2CH2CH2}].  相似文献   

9.
The products of the photolysis of a number of platinacyclopentanes in solution at 25°C under a variety of conditions have been determined. With [I2PtCH2CH2CH2CH2(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 [ICH3PtCH2CH2CH2(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 [PtCH2CH2CH2CH2(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   

10.
The phosphine Ph2PCH2CH2Cl reacts with fac-[XMn(CO)3(dppm)] (X = Cl or Br) in refluxing toluene to give the complexes cis,cis-[XMn(CO)2(dppm)(Ph2PCH2CH2Cl)] (I). Treatment of those species with Na amalgam in THF leads to the alkyl complex [Ph2PCH2CH2Mn(CO)2(dppm)] (II), which does not react with CO under normal conditions but can be converted into cis,cis-[ClMn(CO)2(dppm)(PPh2Et)] by reacting with HCl (g) in ether. If the reduction of I with Na/Hg is carried out in the presence of CO the compound cis-[Ph2PCH2CH2(O)CMn(CO)2(dppm)] (III) is obtained. The latter has also been prepared directly from fac-[BrMn(CO)3(dppm)], Ph2PCH2CH2Cl, and Na/Hg in THF, and characterized by X-ray crystallography. The crystals are monoclinic, space group P21/n; refinement gave R = 0.053 for 2593 reflections with I ? 2.5σ(I). The reaction of the complex fac-[O3ClOMn(CO)3(dppm)] with Ph2PCH2CH2Cl in Cl2CH2 gives the salt fac-[Mn(CO)3(dppm)(Ph2PCH2CH2Cl)]ClO4 which isomerizes to mer-[Mn(CO)3(dppm)(Ph2PCH2CH2Cl)]ClO4 in boiling butanol. Both cationic carbonyl complexes give the acyl species III upon reduction with Na amalgam.  相似文献   

11.
The interaction of azobenzene and MnR(CO)5 (R  Me, Et, CH2Ph, CH2-C6Me5, COCF3, COCH2C6F5, COCH2OPh, Ph or C6F5) affords Mn(C6H4NNPh)-(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 Mn(C6H4CH2PMe2)-(CO)3[PMe2(CH2Ph)] (two isomers) and Mn(C6H4CH2AsMe2(CO)4 have been obtained on treatment with EMe2(CH2Ph) (E  P and As, respectively).  相似文献   

12.
Treatment of [{Ir(COD)(μ-Cl)}2] with excess of the electron-rich olefin [CN(Ar)(CH2)2NAr]2 (abbreviated as (LAr)2, Ar = C6H4Me-p or C6H4OMe-p) affords the ortho-metallated tricycle [Ir(LAr)3], which for Ar = C6H4Me-p (Ia) with HCL yields [Ir(LAr)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 IrC(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   

13.
The platinacyclopentane derivative [Cl(CH2)3R2P](Cl)PtPR2CH2CH2CH2 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 CCl 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 CCl bond to rhodium occurs under formation of the phospharhodacyclopentane [CI(CH2)3R2P] Cl2(OC)-RhPR2CH2CH2CH2 (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   

14.
The secondary phosphite OCH2CMe2CH2OP(O)H reacts with chlorobis(cyclooctene) rhodium(I) dimer to give RhX(R2POHOPR2)2(R2POH) (X=H, Cl) and RhCl2(R2POHOPR2)(R2POH)2 where R2PO = OCH2CMe2CH2PO. The iridium analogue yields corresponding products. The phosphite reacts with bis-(cyclooctene) pentan-2,4-dionatorhodium(I)to give Rh(R2POHOPR2)3 and with the corresponding iridium complex to produce Ir(acac)(R2POHOPR2)2. Some of the complexes act as catalysts or catalytic precursors for the stereoselective reduction of 4-t-butylcyclohexanone.  相似文献   

15.
In the 1H NMR spectrum of the complex [Os3H3(CO)9CC(CH2CH2]+ 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 187Os1H 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 CC(CH2)2CH2 axis in a tilted structure, with concomitant rotation of the Os3H3(CO)9 moiety.  相似文献   

16.
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 C5H5Fe (CO) [(C6H5)2PN (CH2CH3) CH (C6H5)] and C5H5Fe (CO) [(C6H5)2 PN (CH2C6H5)CH(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)2PNC(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   

17.
The gaseous products of the photolysis at 25°C of the platinacyclobutane compounds [X2PtCH2CH2CH2(N-N)] where X = Cl, Br and N-N = 1,10-phenanthroline, 2,2′-bipyridine, (CH2NMe2)2, (C5H5N)2 in several solvents, in the absence and presence of various additives, have been determined. With solvents of relatively low dielectric constant (e.g. CH2Cl2), over 85 mol % of the hydrocarbon products was propene, the formation of which appears to involve a direct transfer of a hydrogen atom between neighbouring groups in the ring. With solvents of relatively high dielectric constant (MeCN, Me2SO) in the presence of species, e.g. I?, SbPh3, having a high trans effect, cyclopropane is the main volatile product. The effect of added halide ion and of the mixed solvents Me2SO/PhMe and Me2SO/PhSH indicates that ionisation of the platinacyclobutane and the formation of platinum substituted propyl ion-radicals precede the formation of cyclopropane (and the small amounts of ethylene produced).The photolysis of [X2PtCH2CH2CH2(MeCN)2] in methyl cyanide solution in the presence of Et3RNX′ (X′ = Cl, R = H; X′ = Br, R = Et) gives appreciable amounts of ethylene in the products (up to 25 mol %). It is suggested that the halide ions add to the platinum to give negatively charged platinacyclobutane species, the photodecomposition of which may give C2H4.  相似文献   

18.
Reactions between MX(PPh3)2(η-C5H5) (M = Ru, X = Cl; M = Os, X = Br) and 2-CH2CHC6H4PPh2 afford MX(η2-CH2CHC6H4PPh2)(η-C5H5); the Os complex is obtained in two isomeric forms. The X-ray structure of the major isomer shows the CC double bond (OsC, 2.214, 2.195 Å; CC, 1.57 Å) is almost coplanar with the OsBr vector, with the terminal C cis to Br; the minor isomer is assumed to have the alternative, more sterically congested conformation, with the β-C cis to Br. The chlororuthenium complex reacts with NaOMe/MeOH to give the corresponding hydrido complex, which also exists as two isomers in solution; reaction of this complex with CS2 gives the expected dithio acid derivative Ru(S2CCHMeC6H4PPh2)(η-C5H5), together with small amounts of a complex assumed to be Ru[S2C(CH2)2C6H4PPh2](η-C5H5). The X-ray structure of the major product reveals an unusual η3-S2C mode of coordination of the dithio acid fragment (RuS, 2.418, 2.426(1) Å; RuC 2.175(4) Å). Crystals of OsBr(η2-CH2CHC6H4P)Ph2)( η-C5H5) are monoclinic, space group P21/n, with a 12.696(2), b 21.719(6), c 15.929(3) Å, β 79.77(2)°, Z = 8; 2867 data (I > 2.5σ(I)) were refined to R = 0.040, Rw = 0.044. Crystals of Ru(η3-S2CCHMeC6H4PPh2)(η-C5H5) are orthorhombic, space group Pbca, with a 8.921(2), b 15.982(9), c 32.216(5) Å, Z = 8; 1685 data (I > 2.5σ(I)) were refined to R = 0.027, Rw = 0.030.  相似文献   

19.
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-Cl2IrH[CH2CMe2CH2P(CH2CMe3)2][P(CH2 (I) [t-BuP(CH2CMe3)2]2H2Ir-μ-Cl2IrH[CH2CMe2CH2PBut(CH2CMe3)][t-BuP(CH2CMe3)2] (II), and [(t-Bu2PCH2CMe2CH2)HIrCl]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   

20.
η5-C5H5(CO)2FeNa reacts with the benzimide chlorides C6H5(Cl)CNR (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)FeC(C6H5)N(CH3)C(C6H5)NCH3PF6 (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 CN 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   

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