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1.
Henri Brunner Gundelinde Kerkien Joachim Wachter 《Journal of organometallic chemistry》1982,224(3):295-300
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
2.
D.A. Lemenovskii V.P. Fedin A.V. Aleksandrov Yu.L. Slovohotov Yu.T. Struchkov 《Journal of organometallic chemistry》1980,201(1):257-268
Electron-acceptor properties of bis-niobocenes (η5-C5H4Y)(H)b(H)(η5-C5H4Y) with X Y H and XY SiMe2OSiMe2have been investigated. Bis-niobocenes are shown to readily add two electrons forming stable salts of the corresponding dianions [(η5-C5H4Y)(H)Nb(η5 : η1- C5H3X)2Nb(H)(η5-C5H4Y)]2-. The surplus electrons can be removed to give quantitative regeneration of initial neutral bis-niobocenes. The crystal and molecular structure of the title compound has been determined; R 0.044, interatomic distance are Nb…Nb 3.93, NbH 1.62, average NbC(π) 2.36, NbC(σ) 2.31 Å, other distances correspond to the usually observed values. Unlike the neutral bis-niobocenes, there is no direct metalmetal bond in the dianionic structures. This conclusion is supported by electronic spectra of neutral and dianionic species. 相似文献
3.
The novel λ4-thia-λ5-phospha-h2-manganabicyclo[2.2.1]heptadienes (OC)3Mn[] (R1 = CH3, C6H5; R2 = CO2CH3, CO2C2H5, CO2C6H11) are formed by action of the activated alkynes R2C CR2 on the heterocycles [(OC)4MnPR12S]2 via the isolable, five-membered heterometallacyclopentadienes (OC)4(R2). The compound with R1 = CH3 and R2 = CO2CH3 crystallizes in the triclinic space group P with Z = 2 and separates quantitatively the thiophene derivative under CO pressure or by reaction with (NH4)2Ce(NO3)6. The use of various acetylenes and of acetylenes with different alkyl groups yields the unsymmetric substituted manganabicycloheptadienes (OC)3Mn[] (R2 = CO2CH3, R3 = R4 = CO2C2H5; R2 = R4 = CO2CH3, R3 = H). With propionic acid methylester the alkyne insertion proceeds regiospecifically. With Raney nickel selective S elimination under ring contraction and formation of the λ4-phospha-h2-manganabicyclo[2.1.1]hexenes (OC)3Mn[R12] (R1 = CH3: R2 = R3 = CO2CH3, CO2C2H5; R2 = CO2CH3, R3 = H; R1 = C6H5: R2 = R3 = CO2C2H5) occurs. (OC)3Mn[(CH3)2] (R2 = R3 = CO2CH3) crystallizes in the monoclinic space group P21/m with Z = 2. The IR and NMR spectra of the heterocycles are discussed in detail. 相似文献
4.
Ekkehard Lindner Faouzi Bouachir Riad Fawzi Dieter Hubner 《Journal of organometallic chemistry》1982,235(3):345-352
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
5.
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
6.
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
7.
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
8.
F.Y. Petillon F. Le Floch-Perennou J.E. Guerchais D.W.A. Sharp Lj. Monojlovic-Muir K.W. Muir 《Journal of organometallic chemistry》1980,202(1):23-37
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
9.
Hans-Peter Abicht Peter Lehniger Kurt Issleib 《Journal of organometallic chemistry》1983,250(1):609-616
The complexes of type R2)2 (M = Pd, Pt) are readily deprotonated by n-Buli under various conditions yielding μ-C-bis-dilithiated species. The resulting carbanions are attacked by the electrophiles Mel, Me3SiCl and Ph2PCl to form the corresponding disubstituted derivatives. The reaction with AuCl . PPh3 yields heterobimetallic complexes with two different MC σ-bonds. The compounds obtained are analytically and spectroscopically characterized. 相似文献
10.
The distribution of La3+ and Ca2+ over the cation sites in Ca2La8(SiO4)6O2 was determined by single-crystal X-ray diffraction. Ca2La8(SiO4)6O2 has the apatite structure, and all available evidence indicates that the space group is , thus precluding a completely ordered structure. The 6h lattice sites are occupied by La3+. In contrast, the 4f sites are occupied equally by La3+ and Ca2+ ions. Consideration of the properties of the La3+ and Ca2+ ions suggests that this distribution is thermodynamically favored for this composition. A simple Ising model suggests ordered columns. These would not be precluded by space group , if the correlation between adjacent columns were random. 相似文献
11.
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
12.
Michael I. Bruce Trevor W. Hambley Michael R. Snow A.Geoffrey Swincer 《Journal of organometallic chemistry》1984,273(3):361-376
Reactions between MX(PPh3)2(η-C5H5) (M = Ru, X = Cl; M = Os, X = Br) and 2-CH2CHC6H4PPh2 afford Ph2)(η-C5H5); the Os complex is obtained in two isomeric forms. The X-ray structure of the major isomer shows the CC double bond (OsC, 2.214, 2.195 Å; CC, 1.57 Å) is almost coplanar with the OsBr 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 Ph2)(η-C5H5), together with small amounts of a complex assumed to be Ph2](η-C5H5). The X-ray structure of the major product reveals an unusual η3-S2C mode of coordination of the dithio acid fragment (RuS, 2.418, 2.426(1) Å; RuC 2.175(4) Å). Crystals of OsBr(η2-CH2CHC6H4P)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 Ph2)(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
13.
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
14.
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
15.
Use of Nd3+, Eu3+, and Gd3+ as local structural probes allows the determination of the rare earth positions in the NaxSr3?2xLnx(PO4)2 (Ln = La to Tb) and KCaLn(PO4)2 phases (Ln = rare earth). Moreover, a common feature of both series is a particularly high splitting of the excitation and levels of the Gd3+ ions. 相似文献
16.
FeIIFeIII2F8(H2O)2 and MnFe2F8(H2O)2, grown by hydrothermal synthesis (), crystallize in the monoclinic system with cell dimensions (Å): a = 7.609(5), b = 7.514(6), c = 7.453(4), β = 118.21(3)°; and a = 7.589(6), b = 7.503(8), c = 7.449(5), β = 118.06(3)°, and space group . The structure is related to that of . It is described in terms of perovskite type layers of Fe3+ octahedra separated by Fe2+ or Mn2+ octahedra, or in terms of shifted hexagonal bronze type layers. Both compounds present a weak ferromagnetism below TN (157 and 156 K, respectively). Mössbauer spectroscopy points to an “idle spin” behavior for FeIIFeIII2F8(H2O)2: only Fe3+ spins order at TN, while the Fe2+ spins remain paramagnetic between 157 and 35 K. Below 35 K, the hyperfine magnetic field at the Fe2+ nuclei is very weak: Hhf = 47 kOe at T = 4.2 K. For MnFe2F8(H2O)2, Mn2+ spin disorder is expected at 4.2 K. This “idle spin” behavior is due to magnetic frustration. 相似文献
17.
《Polyhedron》2001,20(9-10):1089-1095
18.
The cyclometallation of p-RC6H4CHNCH2C6H2, (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 [CH2C6H5)]2, derived from 1H NMR spectra, are different from those reported previously. Reaction of these compounds with PEt3 gives the compounds [PdX(p-RC6H3CHNCH2C6H5)(PEt3)2] but with an excess of PPh3 only the complexes [CH2C6H5)(PPh3)] are formed. 相似文献
19.
20.
and -but-2-ene oxides undergo SN2 opening with the lithium enolate derived from [(η5-C5H5)Fe(CO)(PPh3)COCH2CH3] in the presence of BF3·OEt2; preferential opening occurs where the enolate configuration at iron matches that of the epoxide carbon being attacked. 相似文献