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1.
Reaction of C5H4(SiMe3)2 with Mo(CO)6 yielded [(η5-C5H3(SiMe3)2)Mo(CO)3]2, which on addition of iodine gave [(η5-C5H3(SiMe3)2Mo(CO)3I]. Carbonyl displacement by a range of ligands: [L P(OMe)3, P(OPri)3,P(O-o-tol)3, PMe3, PMe2Ph, PMePh2, PPh3, P(m-tol)3] gave the new complexes [(η5-C5H3(SiMe3)2 MO(CO)2(L)I]. For all the trans isomer was the dominant, if not exclusive, isomer formed in the reaction. An NOE spectral analysis of [(η5-C5H3(SiMe3)2)Mo(CO)2(L)I] L PMe2Ph, P(OMe)3] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon [L P(OMe)3] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe3 group) being the more stable isomer for L P(OMe)3. 相似文献
2.
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
3.
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
4.
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
5.
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
6.
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
7.
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
8.
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
9.
Stuart R. Berryhill 《Journal of organometallic chemistry》1989,370(1-3):C1-C4
The silyl group migration observed upon treating (R)(+)-(η5-C5H5)Fe(CO)2-SiMePh(1-Np) with n-BuLi occurs with retention of configuration at silicon. The anion resulting from the migration, (η5-C5H4SiMePh(1-Np))Fe(CO)2Li, is alkylated with MeI to give (R)-(−)-(η5-C5H4SiMePh(1-Np))Fe(CO)2Me (II). Compound II is independently prepared from (η5-C5H5)Fe(CO)2Me. A concerted mechanism for the migration involving frontside nucleophilic attack at silicon is suggested. 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.
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
12.
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
13.
Cp2MoH2 reacts with methyl acrylate in the presence of acetylenes (L = C2H2, C2Me2, HCCtBu, HCCSiMe3, C2(SiMe3)2, HCCCH2OMe, HCCCH2NMe2) to form acetylene complexes Cp2Mo(L) 5. Protonation takes place with CF3CO2H at −80°C to give short-lived cations [Cp2MoH(L)+ (8) (L = C2Me2, HCCSiMe3, C2(SiMe3)2). The structure of [Cp2MoH{η2-C2(SiMe3)2}]PF6(9) was determined by an X-ray diffraction study. 相似文献
14.
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
15.
Roy L. Beddoes Jonathan R. Hinchliffe David Moorcroft Mark W. Whiteley 《Journal of organometallic chemistry》1998,560(1-2)
Reaction of [MX(CO)2(η7-C7H7)] (M=Mo, X=Br; M=W, X=I) with two equivalents of CNBut in toluene affords the trihapto-bonded cycloheptatrienyl complexes [MX(CO)2(CNBut)2(η3-C7H7)] (1, M=Mo, X=Br; 2, M=W, X=I). The X-ray crystal structure of 2 reveals a pseudo-octahedral molecular geometry with an asymmetric ligand arrangement at tungsten in which one CNBut is located trans to the η3-C7H7 ring. Treatment of 2 with tetracyanoethene results in 1,4-cycloaddition at the η3-C7H7 ring to give [WI(CO)2(CNBut)2{η3-C9H7(CN)4}], 3. The principal reaction type of the molybdenum complex 1 is loss of carbonyl and bromide ligands to afford substituted products [MoBr(CNBut)2(η7-C7H7)] 4 or [Mo(CO)(CNBut)2(η7-C7H7)]Br. Reaction of [MoBr(CO)2(η7-C7H7)] with one equivalent of CNBut in toluene at 60°C affords [MoBr(CO)(CNBut)(η7-C7H7)], 5, which is a precursor to [Mo(CO)(CNBut)(NCMe)(η7-C7H7)][BF4], 6, by reaction with Ag[BF4] in acetonitrile. In contrast with the parent dicarbonyl systems [MoX(CO)2(η7-C7H7)], complexes of the Mo(CO)(CNBut)(η7-C7H7) auxiliary, 5 and 6, do not afford observable η3-C7H7 products by ligand addition at the molybdenum centre. 相似文献
16.
Valerie F. Allen Ronald Mason Peter B. Hitchcock 《Journal of organometallic chemistry》1977,140(3):297-307
X-ray crystallographic analyses of H2Os3(CO)10, H(SC2H5)Os3(CO)10 and (OCH3)2Os3(CO)10 are reported. Although hydrogen atom positions have not been located, the essential isostructural nature of the three commplexes establishes the hydride ligands as bridging two metal atoms, separated by 2.670 Å, with a formal bond order of two; the bridging hydrido- and thiolato-ligands span an osmium---osmium bond of length 2.863 Å and formal bond order one; the two μ-methoxy ligands bridge two metal atoms separated by 3.078 Å which, by simple 18 electron rule counting, has a metal---metal bond order of zero. Some general comments are made on the structures of polynuclear transition metal carbonyls. 相似文献
17.
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
18.
T. M. Polyanskaya M. K. Drozdova V. V. Volkov K. G. Myakishev 《Journal of Structural Chemistry》2009,50(2):368-372
A new compound [MNII(Phen)3]2+(B6H7)2− is synthesized; its crystal structure is studied by XRD at 100 K. Crystallographic data: C36H38B12N6Mn, M = 739.39, triclinic symmetry, space group P
, unit cell parameters: a = 10.3131(3) ?, b = 13.4839(4) ?, c = 15.1132(4) ?; α = 97.696(1)°, β = 108.324(1)°, γ = 102.211(1)°; V = 1903.9(1) ?3, Z = 2, d
calc = 1.290 g/cm3. The structure is solved by direct and Fourier methods and refined by full-matrix LSM in the anisotropic (isotropic for hydrogen
atoms) approximation to the final factor R
1 = 0.036 for 10169 I
hkl
≥ 2σ
I
(Bruker-Nonius X8 APEX CCD diffractometer, λMoK
α). The structure contains two crystallographically different anions.
Original Russian Text Copyright ? 2009 by T. M. Polyanskaya, M. K. Drozdova, V. V. Volkov, and K. G. Myakishev
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 381–385, March–April, 2009. 相似文献
19.
The mechanism of the addition of tetrachloromethane to alkenes in the presence of [Cr(CO)3(η-C10H8)]
The title reaction has been examined in detail and is shown to proceed via a non-chain catalysed mechanism involving free radical intermediates. 相似文献
20.
The complex [MoW(μ-CC6H4Me-4)(CO)2(η7-C7H7)(η5-C2B9H10Me)] reacts with diazomethane in Et2O containing EtOH to afford the dimetal compound [MoW(OEt)(μ-CH2){μ-C(C6H4Me-4)C(Me)O}(η7-C7H7)(η5-C2B9H10Me)]. The structure of this product was established by X-ray diffraction. The Mo---W bond [2.778(4) Å] is bridged by a CH2 group [μ-C---Mo 2.14(3), μ-C---W 2.02(3) Å] and by a C(C6H4Me-4)C(Me)O fragment [Mo---O 2.11(3), W---O 2.18(2), Mo---C(C6H4Me-4) 2.41(3), W---C(C6H4Me-4) 2.09(3), Mo---C(Me) 2.26(3) Å]. The molybdenum atom is η7-coordinated by the C7H7 ring and the tungsten atom is η5-coordinated by the open pentagonal face of the nido-icosahedral C2B9H10Me cage. The tungsten atom also carries a terminally bound OEt group [W---O 1.88(3) Å]. The 1H and 13C-{1H} NMR data for the dimetal compound are reported and discussed. 相似文献