共查询到20条相似文献,搜索用时 31 毫秒
1.
Jeffrey L. Petersen 《Journal of organometallic chemistry》1979,166(2):179-192
The hydrolysis of (η5-C5H5)2Zr(SC6H5)2 was shown previously by IR spectroscopy to produce an oxo-bridged complex. The molecular structure of this material has been determined by X-ray diffraction methods and consists of two (η2-C5H5)2Zr(SC6H5) units linked by an oxo bridge. The ZrOZr bond is nonlinear at 165.8(2)° with a Zr?Zr interatomic separation of 3.902(1)Å. The two independent SZrO bond angles of 98.7(1) and 103.3(1)° are consistent with a d° electronic structure for each zirconium atom. The relatively short ZrO distances of 1.968(3) and 1.964(3) Å support the presence of partial double-bond character arising from the donation of electron density from filled pπ-orbitals on the oxygen atom to unfilled d-orbitals on the electron deficient d0 metal atoms. This bonding feature requires based upon orbital symmetry arguments that the (ML)2O molecular core in [(η5-C5H5)2ML]2O complexes must be nonplanar with a dihedral angle between the two LMO planes less than 90°. For [(η5-C5H5)2Zr(SC6H5)]2O, dihedral angle of 61.7° was observed. The compound crystallizes in an orthorhombic space group, Pbca, with refined lattices parameters a 16.458(4), b 20.281(5), and c 17.016(4) Å. Full-matrix least-squares refinement of 2613 diffractometry data I > σ(I) led to a final discrepancy index R(F02) = 0.044. 相似文献
2.
B. Cetinkaya P.B. Hitchcock M.F. Lappert S. Torroni J.L. Atwood W.E. Hunter M.J. Zaworotko 《Journal of organometallic chemistry》1980,188(3):C31-C35
The 2,6-di-t-butyl-4-methylphenoxo ligand (ArO?) is ambidentate, giving rise to the O-bonded 15-electron d1 [Ti(η-C5H5)2OAr] and the η5 -[C(2)-C(6)]-bonded 18-electron d8 complex [Rh(ArO-η5)(PPh3)2], obtained from [{Ti(η-C5H5)2Cl}2]-LiO Ar and [Rh{N(SiMe3)2}(PPh3)2]-ArOH, respectively; the average TiC(η) distance is 2.362(10) Å, TiO 1.892(2) Å, and O:C(of Ar) 1.352(3) Å, and TiOC 142.3(2)°; in the RhI complex, C(2)C(6) are coplanar (with CC(av.) 1.38(2) Å). C(1)O 1.28 Å, and Rh to C(2) C(6) bond lengthsare in the range 2.19–2.65 Å. 相似文献
3.
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
4.
Pangbu Hong Katsuyuki Aoki Hiroshi Yamazaki 《Journal of organometallic chemistry》1978,150(2):279-293
The diphenylacetylene-cobalt complex, η5-C5H5Co(PPh3)(PhCCph) (I) reacted with alkyl diazoacetates (II, alkyl = methyl, ethyl, and t-butyl) at room temperature to give two isomers of the mononuclear cobalt complex, η5-C5H5Co- (PhC2Ph)(CHCO2R)2 (III and IV) and two isomers of the dinuclear cobalt complex [η5-C5H5Co(PhC2Ph)(CHCO2R)]2 (V and VI).The complexes III and IV are diene complexes, syn,syn- and syn,anti- (dialkyl 2,3-diphenylmuconate)-η5-cyclopentadienylcobalt, respectively. The structure of Vb (R = C2H5) was determined by X-ray diffraction as η-[1–3-η3 : 1,4,5-μ3- 1,6-bis(ethoxycarbonyl)-2,3,4,5-tetraphenylhexa-2,4-diene-1,1-diyl]bis(η5-cyclopentadienylcobalt)(CoCo. The complex VI is the bis(η3-allyl)cobalt complex, μ-[1–3-η3 : 4–6η3-1,6-anti,anti-bis(alkoxycarbonyl)-2,3,4,5,-tetraphenylhexa- 1,3,5-triene]bis(η5-cyclopentadienylcobalt)(CoCo) according to its 1H NMR spectrum.The formation of these products was rationalizes in terms of a cobaltacyclobutene intermediate. 相似文献
5.
《Journal of organometallic chemistry》1987,319(1):9-27
A large variety of (η5-borole)cobalt complexes have been prepared starting with η-(CO)2[Co(CO)(η5-C4H4BR)]2(CoCo) (IIIa: R = Me, IIIb: R = Ph), including inter alia, the sandwich complexes CpCo(η5-C4H4BR) (VIIa, b), the triple-decked complexes η-(η5-C4H4BR)[Co(η5-C4H4BR)]2 (VIIIa, b) and μ-(η5-C4H4BR)(FeCp)[Co(η5-C4H4BR)] (X, R = Ph), the dinuclear complex μ-(CO)2[Fe(CO)Cp][Co(CO)(η5-C4H4BPh)](FeCo) (IX), and salts M[Co(η5-C4H4BR)2](XVa, b: M = Na; XVIa, b: M = NMe4; XVII: M = Cs, R = Ph). The anions [Co(η5-C4H4BR)2]− readily undergo stacking reactions to form multiple-decked complexes such as the triple-decker compounds μ-(η5-C4H4BR)[Mn(CO)3][Co(η5-C4H4BR)] (XIIa, b), μ-(η5-C4H4BR)[Co(η5-C4H4BR)][Rh(η-1,5-COD)] (XVIII), [NMe3Ph][μ-η5-C4H4BPh){Cr(CO)3}{Co(η5-C4H4BPh)}] (XX), and the quadruple-decker complex Ru[μ-(η5-C4H4BR)Co(η5-C4H4BR)]2 (XXI). The monofacially bound η5-borole ligands in VIIb and VIIIb shows regiospecific H/D exchange, at the α position of the boron, on treatment with CF3CO2D at room temperature. VIIb undergoes a Friedel-Crafts substitution to give the 2-acetyl derivative XXIV with MeCoCl/SnCl4 in CH2Cl2 at room temperature.The structure of VIIIa, as determined by X-ray diffraction studies is that of a typical triple-decker compound with nearly coplanar rings. The three borole rings form a helix with torsional angles of 59.8 and 72.2°. All intra-ring bond distances of the central ligand are longer than those of the outer ligands. The metal-ligand interaction is somewhat stronger for the outer ligands than for the central ligand. 相似文献
6.
《Polyhedron》2001,20(15-16):2083-2088
New ferrocenyl-based bimetallic cationic compounds of the type of (E)-[CpFe(η5-C5H4)(CHCH)(C6H4)CNRuCp(PPh3)2]X (X=PF6, BF4) and of (E)-[CpFe(η5-C5H4)(CHCH)(C6H4)CNFeCp(CO)2]PF6 have been obtained and characterized. The crystal structure of (E)-[CpFe(η5-C5H4)(CHCH)(C6H4)CNRuCp(PPh3)2]BF4 has been established by means of X-ray diffractometry. The NLO responses of the compounds have been studied by the hyper-Rayleigh scattering technique and the hyperpolarizability is found to be dependent on the nature of the counterion. 相似文献
7.
[Co(R-η-C3H4)(η-C5H5)I] is a good precursor for the preparation of some new cationic complexes as the iodide can easily be replaced; thus addition of PEt3 to the iodo-complex (R H) gives [Co(η-C3H5)(η-C5H5)(PEt3)]+. The reactions of [Co(R-η-C3H4)(η-C5H5))I] (R H or 2-Me) with AgBF4 give solutions containing the coordinatively unsaturated species [Co(R-η-C3H4)(η-C5H5)+. The presence of traces of water leads to the formation of [Co(R-ηC3H4)-(η-C5H5)(H2O)]+. The addition of monodentate ligands L PEt3 PPh3, AsPh3, SbPh3, CNCH3 and bidentate ligands LL Ph2PCH2CH2PPh2(dppe) and o-C6H4(AsMe2)2(diars), gives, respectively mononuclear [Co(2-Me-ηC3H4)-(η-C5H5)L]+ and binuclear ligand-bridged [(2-Me-ηC3H4)(η-C5H5)CoLLCo(2-Me-ηC3H4)(η-C5H5))]2+ complexes. Crystals of [Co(2-Me-ηC3H4)(η-C5H5)-(H2O)]+[BF4]- are monoclinic, space group P21/c, with a 7.858(3), b 10.262(4), c 15.078(4) Å, β 98.36(1)°. The molecular structure contains the cobalt atom bonded to planar 2-Me-allyl and cyclopentadienyl substituents, which are almost parallel with the H2O molecule in a staggered conformation with respect to the 2-Me group. 相似文献
8.
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
9.
Colin Eaborn 《Journal of organometallic chemistry》1982,238(2):C15-C16
The metalmetal double-bonded μ-alkyne complex [Ru2(μ-CO)(μ-C2Ph2) (η-C5H5)2] (1) reacts with diazomethane at 0°C to yield Ru2(CO)(η-CH2) {μ-C(Ph)C(Ph)CH2} (η-C5H5)2] (2) incorporating two methylene units, one bridging the metal atoms and one linked with the alkyne. Upon heating, a second carboncarbon bond formation occurs to link the methylene groups and give [Ru2(CO)(μ-CO) {μ-C(Ph)C(Ph)C(H)Me} (η-C5H5)2 (3); the structures of 1 and 2 were established by X-Ray diffraction. 相似文献
10.
The N-sulfinylsulfonamides R′S(O)2NSO (R′ = CH3, p-CH3C6H4) insert into the FeR bonds of η5-C5H5Fe(CO)2R (R = CH3, CH2C6H5) to afford η5-C5H5Fe(CO)2N[S(O)2R′][S(O)R]. These products undergo oxidation by m-ClC6H4C(O)-OOH to η5-C5H5Fe(CO)2N[S(O)2R′][S(O)2R] and rearrange on storage to η5-C5H5Fe(CO)2S(O)[NS(O)2R′]R. Reaction between the η5-C5H5Fe(CO)2R and CH3S(O)2NSNS(O)2CH3 leads to the insertion products η5-C5H5Fe(CO)2N-[S(O)2CH3][S(R)NS(O)2CH3]. 相似文献
11.
The preparation of the compounds {(η-C5H5)MoX}2{μ-(η5-C5H4-η5-C5H4)} (X = Me, PhCH2, Me3SiCH2, Br) and {(η-C5H5)MoY2}2{μ-(η5-C5H4-η5-C5H4)}, (Y = H, I, SMe, S-n-Bu) is described. Photolysis of {(η-C5H5)MoH}2 {μ-(η1:η5 -C5H4)}2 and {(η-C5H5)MoH}2{(η5-C5H4-η5-C5H4)} in benzene leads to a compound of stoichiometry C20H18Mo2. 相似文献
12.
The new compounds {(η-C5H5WX)[μ-(σ, η-C5H4)]}2, where X = Cl, Br or I are described. The known hydride X = H, protonates and rearranges giving the new cation {(η-C5H5)WH}2, (μ-H)[μ-C5(η-C5H4-η-C5H4)]+. 相似文献
13.
Jack L. Davidson William F. Wilson Ljubica Manojlović-Muir Kenneth W. Muir 《Journal of organometallic chemistry》1983,254(1):C6-C10
η2 -Vinyl complexes [MCl{η2 -C(CF3)C(CF3)L} (CF3CCCF3)(η5 -C5H5)] (M = Mo, W: L = tertiary phosphine or phosphite or pyridine) have been shown by NMR and X-ray diffraction studies to exist in two distinct isomeric forms which exhibit (a) different orientations of the η2 -vinyl ligand (b) different configurations at the asymmetric carbon atom of the η2 -vinyl ligand: variable temperature NMR studies reveal fluxional behaviour thought to involve reversible inversion of configuration at this carbon atom. 相似文献
14.
Bruno Therrien Ludovic Vieille-Petit Petr Štěpni?ka Georg Süss-Fink 《Journal of organometallic chemistry》2004,689(15):2456-2463
A series of arene-ruthenium complexes of the general formula [RuCl2{η6-C6H5(CH2)2R}L] with R=OH, CH2OH, OC(O)Fc, CH2OC(O)Fc (Fc=ferrocenyl) and L=PPh3, (diphenylphosphino)ferrocene, or bridging 1,1′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene-ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl3 · nH2O to afford [RuCl2{η6-C6H5(CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl2{η6-C6H5(CH2)3OH}L] to give [RuCl2{η6-C6H5(CH2)3OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl2{η6-C6H5(CH2)3OH}(PPh3)] shows that the presence of a CH2CH2CH2OH side-arm allows [RuCl2{η6-C6H5(CH2)3OH}(PPh3)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system. 相似文献
15.
《Journal of organometallic chemistry》1990,393(1):C6-C9
The zirconium silyl complex CpCpZr[Si(SiMe3)3]Me (1; Cp = η5-C5H5; Cp = η5-C5Me5) reacts with nitriles RCN (R = Me, CHCH2, Ph) to form the azomethine derivatives CpCpZr[NC(R)Si(SiMe3)3]Me (2, R = Me; 3, R = CHCH2; 4, R = Ph). Pyridine reacts with 1 to give a 75% yield of CpCpZr[NC5H5Si(SiMe3)3]Me (5), which results from 1,2-addition of the ZrSi bond of 1 to pyridine. These reactions provide the first examples of nitrile and pyridine insertions into a transition metal-silicon bond. The related silyl complexes Cp2Zr[Si(SiMe3)3]Me and CpCpZr[Si(SiMe3)3]Cl are much less reactive toward nitriles and pyridine. 相似文献
16.
Theoretical Study on Inverse Sandwich Complexes [E-C{5-n}H{5-n}Nn-E]+ and [E-C{5-n}H{5-n}Pn-E]+ (n=1, 2, 3; E=Al,Ga, In,Tl)
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The inverse sandwiches [E-C{5-n}H{5-n}Nn-E]+ and [E-C{5-n}H{5-n}Pn-E]+ (n=1, 2, 3; E=Al, Ga, In, Tl) with low-valent boron group elements are studied. The (η5,η5) coordinated inverse sandwich [E-C{5-n}H{5-n}Nn-E]+ is unstable in energy or nonexistent. However, the (η5,η5) coordinated [E-C{5-n}H{5-n}Pn-E]+ is not only stable in energy, but also stable against dissociation. The dissoction stability [E-C{5-n}H{5-n}Pn-E]+ with the same E element decreases as the number n increases, while for the certain n number, the dissociation energies with different E elements are close to each other. [E-C4H4P-E]+ has similar dissocition stability to the well-known [E-C5H5-E]+. The inteaction between C{5-n}H{5-n}Pn and lowvalent E element is mainly ionic. Since lone pairs of electrons locate on both E and P atoms, the (η5, η5) coordinated inverse sandwich [E-C{5-n}H{5-n}Pn-E]+ would act as multi electron-donors. 相似文献
17.
《Journal of organometallic chemistry》1995,503(2):C46-C47
The reaction of [Fe(CO)2(PPh3)2{η2-SCNC(O)Ph}] with [Co(η-C5H5)(PPh3)2] in benzene solution at room temperature results in the facile cleavage of the CS bond of the SCNC(O)Ph ligand to give [{Co(η-C5H5)}2{Fe(CO)2(PPh3)}(μ3-S{μ3-CNC(O)Ph}], whereas [Fe(CO)2(PPh3)2(η2-SCNMe)] gives [{Co(η-C5H5)} 22{Fe(CO)(CNMe)(PPh3)(μ3-S)(μ3-CO)]. The structure of [{Co(η-C5H5)}2{Fe(CO)2(PPh3)} (μ3-CNC(O)Ph}] has been confirmed by X-ray diffraction. 相似文献
18.
Reaction of the 16 electron monomer [Co(η5-C5H5)(S2C2{CN}2)] with various tertiary phosphines and phosphites (L) gives readily the 18 electron monomers [Co(η5-C5H5)(S2C2{CN}2)L] which for L = P(OR)3 have J(C55) ca. 6 Hz but J(C55) = 0 for L = PR3. 相似文献
19.
Helmut Werner Hans-Juergen Kraus Ulrich Schubert Klaus Ackermann Peter Hofmann 《Journal of organometallic chemistry》1983,250(1):517-536
The complexes (η5-C5H5)Pd(η1-C5H5)PR3 which are prepared from [Cl(PR3)-Pd]2(μ-OCOCH3)2 and TlC5H5 are fluxional in solution. According to the 1H and 13C NMR spectra at various temperatures, two dynamic processes occur. The process with the higher activation energy is a π/σ (η5/η1) exchange of the two different cyclopentadienyl ligands, whereas the second one with the lower activation energy presumably is a metallotropic rearrangement (1,2-shift). The coalescence temperature for the η5/η1 exchange depends on the size of the phosphine. The X-ray structural analysis of (C5H5)2PdPPri3 proves that it exists as a “frozen” η5 + η1 structure in the crystal with the palladium approximately in a square-planar coordination. The η5-bonded cyclopentadienyl ring shows some unusual bonding patterns which are obviously electronic in nature. EHT-MO calculations for (η5-C5H5)PdCH3(PH3) indicate that in this model system alternating CC distances in the ring and a stronger bond of the metal to one of the five carbon atoms of the C5H5 ligand are to be expected. The calculations suggest that in similar complexes possessing a six-electron donor ligand like C5H5? and a metal fragment which is isolobal to PdCH3(PH3)+, analogous distortions should be observed. Some reactions of the compounds (η5-C5H5)Pd(η1-C5H5)PR3 are described. 相似文献
20.
The complexes (η5-C5H5)Fe(CO)2(η1-acenaphthenyl) (I), (η5-C5H5)Fe(CO)2 (η1-trans-β-deuterioacenaphthenyl) (II), and (η-C5D5)Fe(CO)2, (η1-acenaphthenyl) (XIII) have been prepared and their thermal decomposition studied in vacuo and in refluxing toluene. All three complexes decompose to produce mixtures of acenaphthene (VII), acenaphthylene (VIII), and [C5H5Fe(CO)2]2 (VI). Biacenaphthenyl (IX) is also obtained from the thermolysis of I in toluene. The formation of alkene VIII, and, to a lesser extent, alkane VII is suppressed by external CO. Thermolysis of I in toluene-d8 and of II in vacuo and in toluene produces deuterium-enriched VII. The acenaphthene generated from the decomposition of XIII also contains deuterium. The above observations are accomodated by a mechanistic scheme involving competing β-elimination, ironcarbon bond homolysis to produce the acenaphthenyl radical, and CpH abstraction by an undetermined pathway. 相似文献