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1.
LI Xiu-juan ZENG Zheng-zhi 《高等学校化学研究》2006,22(1):6-10
IntroductionSince K pf[1]discovered that dicyclopenta die-nyltitanium dichloride possesses antitumour action in1979,a large number of cyclopentadienyltitanium com-plexes with different substituents have been synthe-sized[2,3].The experimental data reveal … 相似文献
2.
The mechanism of the transformation of (η5-C5H5)2NbCl2 to (η5-C5H5)2NbH3 by hydridoaluminate reducing agents has been investigated. Results suggest disproportionation of a niobium(IV) hydrite, leading to the trihydride product and a niobium(III) hydridoaluminate, (η5-C5H5)2NbH2AlR2, which in turn is converted to the trihydride on hydrolysis. (η5-C5H5)2NbH2AlH2 has been isolated; deuterium labelling shows that hydrogens exchange between ring and metal-bridging positions in this molecule. 相似文献
3.
Eulalia Ramirez-Oliva Jorge Cervantes Francisco Cervantes-Lee Ramesh N. Kapoor Keith H. Pannell 《Journal of organometallic chemistry》1996,510(1-2):57-62
A transition metal-substituted silylacetylene [(η5-C5H5)Fe(CO)2SiMe2C]2, [FpMe2SiC]2 (I) was synthesized and characterized spectroscopically and structurally. I crystallized in the monoclinic space group P21/n, A = 13.011(3) Å B = 12.912(3) Å, C = 13.175(5) Å, β = 94.95(2). The acetylene linkage is reactive toward Co2(CO)8 to form I. Co2(CO)6 (II) which was also characterized spectroscopically and by single crystal X-ray diffraction. II crystallized in the orthorhombic space group Pbca, A = 17.64(2) Å, B = 14.225(10) Å, C = 24.49(2) Å. 相似文献
4.
Michael I. Bruce Peter Hinterding Edward R. T. TiekinkBrian W. Skelton Allan H. White 《Journal of organometallic chemistry》1993,450(1-2)
Reactions between [Ru(thf)(PPh3)2(η-C5H5)]+ and lithium acetylides have given further examples of substituted ethynylruthenium complexes that are useful precursors of allenylidene and cumulenylidene derivatives. From Li2C4, mono- and bi-nuclear ruthenium complexes were obtained: single-crystal X-ray studies have characterised two rotamers of {Ru(PPh3)2(η-C5H5)}2(μ-C4), which differ in the relative cis and trans orientations of the RuLn groups. Protonation of Ru(CCCCH)(PPh3)2(η-C5H5) afforded the butatrienylidene cation [Ru(C=C=C=CH2)(PPh3)2(η-C5H5)]+, which reacted readily with atmospheric moisture to give the acetylethynyl complex Ru{CCC(O)Me}(PPh3)2(η-C5H5), also fully characterised by an X-ray structural study. 相似文献
5.
Francis J. Timmers W.Robert Scheidt Jay A. Labinger Subhash Baral 《Journal of organometallic chemistry》1982,240(2):153-155
The photoreaction of (η-C5H5)2TaH3 with Mn2(CO)10 gives, inter alia, (η-C5H5)2(CO)Ta(μ-H)Mn2(CO)9, whose crystal structure reveals an open, bent trimetallic framework. Preliminary mechanistic studies show that this and the analogous niobium reaction proceed via a complex sequence of thermal steps following photoinitiation. 相似文献
6.
Salih S. Al-Juaid Peter B. Hitchcock Julian A. Johnson John F. Nixon 《Journal of organometallic chemistry》1994,480(1-2):45-50
The preparation of novel 1-arsa-3,4-diphospholyl and 3-arsa-1,4-diphospholyl anions of the type (C2tBu2AsP2)− is described. Spectroscopic and structural characterisation of mono-and bi-metallic complexes of these anions are also reported. 相似文献
7.
The reductive electrochemistry of compounds of the type CpFe(CO)2L (Cp = η-C5H5, η-C5Me5; L = SP(S)(OEt)2, SP(S)(OiPr)2) has been examined by polarography, cylic voltammetry and coulometry. The first one-electron reduction step leads to a bond rupture process with formation of a mercury compound, [CpFe(CO)2]2Hg, at a mercury electrode and the corresponding dimer species at a platinum electrode. The second reduction step corresponds to the reduction of the dimer [CpFe(CO)2]2, except in the polarographic reduction of pentamethylcyclopentadienyl compounds. 相似文献
8.
A high yield synthesis of the carbonyl dithiocarbamato derivative Fe(CO)2(η2-S2CNMe2)2 and Fe(η2-S2CNMe2)2 by photolysis with visible light of solutions containing Fe2(CO)9 or Fe3(CO)12 and [(η5-C5H5)(CO)3W(η1-SCSNMe2)] is reported. 相似文献
9.
Won Seok Seo Youn Jaung Cho Sung Cheol Yoon Joon T. Park Younbong Park 《Journal of organometallic chemistry》2001,640(1-2):79-84
Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C5H5)CH2(2-C4H3NH) (2) with Ti(NMe2)4 affords bis(dimethylamido)titanium complex [(η5-C5H4)CH2(2-C4H3N)]Ti(NMe2)2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH2(2-C4H3NH)}2C5H4 (4), undergoes an analogous reaction with Ti(NMe2)4 to give [1,3-{CH2(2-C4H3N)}2(η5-C5H3)]Ti(NMe2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
10.
Alberto R. Dias Adelino Galvo M. Helena Garcia Maria J. Villa de Brito 《Journal of organometallic chemistry》2001,620(1-2):276-281
An unexpected trimanganese(I) tetrathiolate-bridged complex, [Mn3(CO)9(μ-SC6H5)4]−, with an incomplete cubane structure, was obtained by thermal reaction of [Mn2(CO)10] with [Mo(η5-C5H5)2(SC6H5)2]. The structure, established by single-crystal X-ray diffraction studies, shows the cation, [Mo(η5-C5H5)2(H)CO]+, directed towards the vacant site of the cubane structure. Possible routes by which the anion and the cation could be formed are discussed. 相似文献
11.
The interaction of [(η5-C5H4But)2YbCl · LiCl] with one equivalent of Li[(CH2) (CH2)PPh2] in tetrahydrofuran gave [Ph2PMe2][(η5-C5H4But)2Li] (1) and [(η5-C5H4But)2Yb(Cl)CH2P(Me)Ph2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph2PMe2][CF3SO3] with two equivalents of (C5H4But)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η5-C5H4But)2Li]− anion. 相似文献
12.
K. O. Kallinen M. Ahlgr n T. T. Pakkanen T. A. Pakkanen 《Journal of organometallic chemistry》1996,510(1-2):37-43
The reaction between Ru3(CO)12 and a cyclic olefin (cis-cyclooctene or trans-cyclododecene) at 100 °C for several hours gives the title compounds (μ-H)2RU3(CO)9(μ3-η2-C8H12) (1), and (μ-H)RU3(CO)9(μ3-η3-C12H19) (2), both of which have been characterized by X-ray diffraction studies, IR and NMR spectral measurements and elemental analysis. The prolonged reaction between Ru3(CO)12 and cis-cyclooctene gives compound HRu3(CO)9(C8H11) (3). Compound 3 has been characterized with IR and NMR spectral analyses. In 1 the cyclooctene ring is linked via a μ3-η2-alkyne type of bonding to the face of the Ru3 cluster. It is formally σ-bonded to two of the three Ru atoms and π-bonded to the third Ru. The two hydrides in 1 are bridging Ru---Ru bonds. In 2 the cyclododecene ring is bonded to the Ru3 face via the μ3-η3-CCHC linkage. There are two formal σ-bonds from the allyl part to the hydrido-bridged Ru atoms and the η3-allyl linkage to the third Ru atom. 相似文献
13.
The reduction of titanocene dithiocyanate in various solvents has been examined using the techniques of polarography, voltammetry, controlled potential electrolysis and cyclic voltammetry. In THF and CH2Cl2, Cp2Ti(NCS)2 undergoes successive one-electron transfer reactions, and by using a combination of electrochemical and EPR techniques it has been possible to confirm the stability of [Cp2Ti(NCS)2]? in these solvents. In DMF, however, an irreversible dimerization follows the first electron transfer. 相似文献
14.
Heinz-Peter Klein Ulf Thewalt Karl Döppert Roberto Sanchez-Delgado 《Journal of organometallic chemistry》1982,236(2):189-195
The trinuclear titanium(IV) complex (π-C5H5)2TiClOTi(π-C5H5)ClOTiCl(π-C5H5)2 · CHCl3 is formed by hydrolysis of (π-C5H5)2TiCl2 at pH > 3.5 and can be isolated in the crystalline state from the reaction of (π-C5H5)2TiCl2 with Ag2O and water in chloroform. Its structure is determined by X-ray analysis. 相似文献
15.
Jonathan P. Blitz Nigel T. Lucas Mark G. Humphrey 《Journal of organometallic chemistry》2002,650(1-2):133-140
The 60-electron tetrahedral clusters W2Ir2(μ-L)(CO)8(η5-C5H4Me)2 [L=dppe (2), dppf (3)] have been prepared from reaction between W2Ir2(CO)10(η5-C5H4Me)2 (1) and the corresponding diphosphine in 52 and 66% yields, respectively. A structural study of 2 reveals that three edges of a WIr2 face are spanned by bridging carbonyls, that the iridium-ligated diphosphine coordinates diaxially and that the tungsten-bound methylcyclopentadienyls coordinate axially and apically with respect to the plane of bridging carbonyls. A structural study of 3 reveals that the dppf ligand bridges an Ir---Ir bond which is also spanned by a bridging carbonyl; tungsten-ligated methylcyclopentadienyl ligands and terminal carbonyls result in electronic asymmetry (17e and 19e iridium atoms) in the electron-precise cluster. Both clusters show two reversible one-electron oxidation processes and an irreversible two-electron reduction; the dppf-containing cluster 3 has a further, irreversible, one-electron oxidation process. UV–vis-NIR spectroelectrochemical studies of the 2→2+→22+ progression reveal the appearance of a low-energy transition on oxidation to 2+ which persists on further oxidation to 22+. 相似文献
16.
The electronic absorption spectrum of (η5-C5H5)Mn(CO)2[C(C6H5)2]shows an intense maximum which is assigned to a MLCT transition in which the empty pπ orbital on the carbene carbon is populated. Upon irradiation of this band, the complex undergoes a decomposition with a disappearance quantum yield Φ = 0.10 ± 0.01 independent of solvent. In the CT excited state, the complex can be roughly described as containing d5 MnII and a diphenylcarbene radical anion ligand C(C6H5)2?. Due to the kinetic lability, the complex decomposes producing a MnII species and the free carbene radical anion, which then undergoes secondary reactions. In addition, small amounts of substitution product are observed. It is proposed that prior to total decomposition of the excited state, a radical pair (η5-C5H5)Mn(CO)2S+/C(C6H5)2?forms (S = solvent). A back electron transfer from C(C6H5)2?to the labile cation competes with decomposition to produce the substituted complex and free carbene. 相似文献
17.
David S. Ginley C. Randolph Bock Mark S. Wrighton Beda Fischer Donald L. Tipton Robert Bau 《Journal of organometallic chemistry》1978,157(1):41-50
Reaction of photogenerated (η5?C5H5)2W2(CO)4 with acetylene at 25°C yields a complex of the formula (η5-C5H5)2W2(CO)4(C2H2). The crystal structure of the complex shows it to have a tetrahedrane-like W2C2 core. The C—C bond distance of the C2H2 unit is 1.33 Å which is close to that of ethylene, considerably longer than the 1.20 Å for acetylenes. The W—W distance is 2.987 Å which is ~0.25 Å shorter than the W—W distance in (η5-C5H5)2W2(CO)6 but longer than that expected for (η5-C5H5)2W2(CO)4. By analogy to the parent (η5-C5H5)2M2(CO)6 species, the near-UV absorption in (η5-C5H5)2M2(CO)4(C2H2) is assigned to a σb → σ* transition. Owing to the shorter M—M bond in the C2H2 adducts, the σb → σ* absorption is at higher energy than in the (η5-C5H5)2M2(CO)6 complexes. 相似文献
18.
Rainer Bartsch Peter B. Hitchcock John F. Nixon 《Journal of organometallic chemistry》1988,340(3):C37-C39
Syntheses of the novel sandwich compounds [Fe(η5-C5H5)(η5-C2R2P3)] and [Fe(η5-C5H5)(η5-C2R2P3)W(CO)5], (R = But), are described. The mode of attachment of the [W(CO)5] fragment in the latter compound has been determined by NMR and single crystal X-ray diffraction studies. 相似文献
19.
The complex Fe(η6-C5H5CMe3)2 crystallizes in the centrosymmetric triclinic space group P
(Ci1; No. 2) with unit cell dimensions of a 8.770(1) Å, b 8.878(1) Å, c 11.991(1) Å, 107.56(1)°, β 90.85(1)°, γ 90.13(1)°, V 890.0(2) Å3 and Z = 2. A full sphere of data was collected on a four-circle diffractometer. The structure was solved and refined to R 7.93% for all 3155 independent reflections and R 4.98% for those 2002 data with | F0 | > 6σ. | F0 |. The molecules lie on crystallographic inversion centers at 0, 0, 0 and 1/2, 0, 1/2; the crystallographic asymmetric unit therefore consists of two independent half molecules. The molecule centered at 0, 0, 0 (molecule “A”) is ordered and well-defined; that centered on 1/2, 0, 1/2 (molecule “B”)is probably disordered, as indicated by larger “thermal parameters” and a greater range of apparent interatomic distances. Discussion em phasizes the geometry of molecule A, which has precise Ci symmetry with Fe(1A)-B(1A) 2.297(4) Å and Fe(1A)-C(ring) distances ranging from 2.057(6) Å to 2.138(4) Å. 相似文献