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1.
Halogens, X2, and HgY2 (X = Cl, Br, I; Y = X, F, NO3, BF4) cleave the metalmetal bonds in [Fe2(η-C5H5)2(CO)4−n(CNMe)n] complexes (n = 0–4). Typically, e.g., when n = 2, X2 electrophiles give [Fe(η-C5H5)(CO)(CNMe)X] (a) and [Fe(η-C5H5)(CO)(CNMe)2]X (b) in relative yields which depend on X, the reaction solvent and n, but HgY2 give equimolar amounts of [Fe(η-C5H5)(CNMe)2Y] (c and [Fe(η-C5H5)(CO)2HgY] only. Hg(CN)2 reacts more slowly than other HgY2, and [Hg(PPh3)2I2] does not react at all. It is suggested that the reactions which give rise to products of type (a), (b) or (c) are all two-electron oxidation which proceed by way of adducts containing μ-CA → X2 or μ-CA → HgX2 groups (Ca = CO or CNMe). One of these adducts has been isolated, namely [Fe2(η-C5H5)2(CNMe)2{μ-CN(Me)HgCl2}2] · CHCl3.  相似文献   

2.
The protonated species [Fe2(η-C5H5)2(CO)2(η-CO){μ-CN(Me)H}]X, [Fe2(η-C5H5)2(CO)(CNMe)(μ-CO){μ-CN(Me)H}][X], and [Fe2(η-C5H5)2(CO)2{η-CN(Me)H}2][X]2 react with one equivalent of AgY. The Ag+ and one H+ act together as a two-electron oxidant. Silver metal is precipitated quantitatively and the substrates cleaved to give mono-nuclear products of the type (a) [Fe(η-C5H5)(CO)(L)X] and [Fe(η-C5H5(CO)(L)Y] or (b) Fe(η-C5H5(CO)(L)(CNMe)][X] (L = CO, CNMe). If X and Y are both coordinating anions such as NO3, I, or Br or the solvent is MeCN products of type (a) are usually obtained with X = Y = MeCN+ if acetonitrile is used as the solvent. However, if either X or Y is a non-coordinating anion such as BF4 or PF6 and methanol is the solvent, the products are usually those of type (b). When X = [p-MeC6H4SO3], both types of products are obtained in significant amounts. If two equivalents of Ph3P are added to the methanol solution of [Fe2(η-C5H5)2(CO)2{-CN(Me)H}2[BF6]2, no reaction takes place until the third equivalent of AgNO3 has been added. The products have been isolated and characterized by analysis and infrared spectroscopy. The previously unreported [Fe2(η-C5H5)2(CO)(CNMe)(η-CO){η-CN(Me)H}] X salts are described for X = BF4, PF6, Br · 2H2O, I · H2O, NO3 · 0.5H2O, and p-MeC6H4SO3.  相似文献   

3.
The salts [Fe2η55-C5H4CH{NMe3)CH(NMe2)C5H4}(CO)2(μ-CO)2][X] (X = I or SO3CF3) are the synthetic precursors to a wide range of [Fe2(η-C5H5)2(CO)2(μ-CO)2] derivatives in which the two cyclopentadienyl ligands are joined by a two-carbon bridge.  相似文献   

4.
The reactions of equimolar amounts of [Fe2(η-C5H5)2(CO)2(CNMe){CN(Me)H}]X and AgY in methanol results in a two-electron oxidation of [Fe2(η-C5H5)2(CO)2(CNMe)2] to give [Fe(η-C5H5)(CO)(CNMe)2]BF4 when either X or Y are the non-coordinating anion BF4, but [Fe(η-C5H5(CO)(CNMe)X] and [Fe(η-C5H5(CO)(CNMe)Y] when both X and Y are potentially coordinating anions such as NO3, Br or I.  相似文献   

5.
6.
Abstract

The trietheylaluminum based ferrocenylalane (η5?C5H5)Fe[η5?C5H4Al2(C2H5)4Cl] was prepared from the reaction of triethylaluminum with chloromercuriferrocene in toluene and characterized by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P 1 with unit cell dimensions a = 9.353(3) Å, b = 10.281(7) Å, c = 11.599(9) Å, α = 79.64(7)°, β = 69.41(6)°, γ = 84.33(4)°, and Z = 2 for Dc = 1.27 g cm?3. Full-matrix least-squares refinement has led to a final R factor of 0.068 based on 1866 independent observed reflections. The two diethylaluminum units are bridged by a chlorine atom and one carbon atom of a cyclopentadienyl group, thus forming an Al-Cl-Al-C ring. The four-membered ring is planar to within 0.02 Å. The Al-Cl distances are 2.404(4) Å and 2.266(5) Å. The Al-Cl-Al angle is 78.9(1)° while the Al-C-Al angle is 91.3(4)°. No significant aluminum-iron interaction is observed (Al… Fe = 3.137(4) Å).  相似文献   

7.
The structure of a new ansa compound, (5-C5H4)CMe2(5-C9H6)TiCl2 (1), was studied by X-ray analysis:a = 15.00(1),b =15.500(5),c = 13.032(4) Å, = 92.66°(4),V = 3025.1(1) Å3, space groupP21/.,R = 0.038. The distorted tetrahedral coordination sphere of the Ti atom is formed by two Cl atoms and two -ligands. It was proposed that the angle () between theC-M direction and the line normal to M-Cp can be considered as one of the geometric parameters characteristic of the structure-properties correlation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 305–308, February, 1995.  相似文献   

8.
Isomeric pairs of silicon-germanium compounds containing a SiGe bond (Me3SiGePh3 (I) and Ph3SiGeMe3 (II); FpSiMe2GeMe3 (III) and FpGeMe2SiMe3 (IV) (Fp = (η5-C5H5)Fe(CO)2); IFpSiMe2GeMe3 (V) and IFpGeMe2SiMe3 (VI) (IFp = (η5-C9H7)Fe(CO)2); IFpSiMe2GePh3 (VII) and IFpGeMe2SiPh3 (VIII) and the complex FcSiMe2GeMe2Fc (IX) (Fc = ferrocenyl) have been synthesized and examined by mass spectrometry.The R3SiGeR′3 compounds I and II exhibit considerable exchange of R groups to produce [R3-nR′nSi]+ and [R′3-nRnGe]+ ion in progressively lesser amounts as n = 1 → 2 → 3. For the metal-substituted complexes containing the grouping FeSiGe fragmentation occurs predominantly via SiGe bond cleavage with formation of ions containing the silylene ligand [FeSiR2]+. Complexes with the FeGeSi backbone undergo preferential scission of the FeGe bond, illustrating the general bond strength trend FeSi > SiGe. Upon direct cleavage of the SiGe bond in R3SiGeR3 compounds, the percentage of the charge carried by [R3Si]+ ions significantly exceeds that carried by [R3Ge]+ ions, reflecting the greater electronegativity of Ge polarizing the SiGe bond.  相似文献   

9.
The crystal and molecular structures of (η5-C5H5)Fe[η5--C5H4CCo3(CO)9] (1), Pna21, α 17.354, b 11.463, c 11.207 Å Z = 4, R = 0.053, Rw = 0.056 for 939 reflections (I>3σ(I)) at 293 K, and (η5-C5H5Fe[η5--C5H4CCo35C5H5)3CH] (2), P21/n, a 13.807(9), b 11.254(4), c 13.991(9) Å, β 99.98(5)°, Z = 4, R = 0.033 and Rw = 0.033 for 3051 observed reflections (I>3σ(I)) at 180 K, have been determined by X-ray methods.The results provide a detailed characterisation of related tricobalt-carbon complexes directly bound to ferrocene residues. In 1 the ferrocenyl moiety tops the pyramidal CCo3 cluster core, while in 2 the CCo3C core is bipyramidal with a ferrocenyl substituent on one capping carbon atom and a hydrogen atom at the other. In both cases the ferrocenyl group is tilted towards one cobalt atom of the cluster core, a distortion believed to be the consequence of the non-degeneracy of the carbyne p(π) orbitals resulting from a cooperative π-interaction between the clusters and the ferrocenyl substituents.  相似文献   

10.
The complex t-Bu(η5-C5H5)FE(CO)2 has been treated with triphenylphosphine in refluxing THF to produce t-BuCO(η5-C5H5)Fe(CO)(PPh3). The large steric bulk of the t-butyl group suggests that this reaction should be faster than the reaction involving the methyl group, and a kinetic investigation illustrates this to be the case. The same steric bulk predicts that the reaction with SO2 should be slow, and indeed we have been unable to effect the related SO2 insertion reaction. Attempts to prepare the corresponding t-Bu(η5-C5H5)W(CO)3 led to formation of the related isobutyl complex.  相似文献   

11.
Antimony is reduced when [SbPh2BrO]2 is treated with Na[Mo(CO)3(η5-C5H5)] to produce [μ-SbPh2]2[Mo(CO)2(η5-C5H5)]2. A structure determination shows diphenylstibido groups bridging between two Mo(CO)2(η5-C5H5) moieties giving a central ‘butterfly’ shaped Sb2Mo2 ring. The cyclopentadiene rings are trans to each other and Mo–Sb and Sb–Sb separations are both short. An iron analogue could not be obtained from [SbPh2BrO]2 and Na[Fe(CO)2(η5-C5H5)] but a mixture of SbPh[Fe(CO)2(η5-C5H5)]2 and SbPh2[Fe(CO)2(η5-C5H5)] was obtained using SbPh2Cl. An X-ray structure for SbPh[Fe(CO)2(η5-C5H5)]2 shows an open stibinidine structure.  相似文献   

12.
13.
Reaction of the novel ruthenacyclopentatriene [(η5-C5H5)Ru(C4Ph2H2)Br] (1) with isocyanides gives the imino-2,5-diphenylcyclopentadiene complexes [(η5-C5H5Ru(η4-C5Ph2H2NR)Br] (2, R = Me, Et, Cy, t-Bu, 2,6-Me2C6H3); a novel fluxional process involving phenyl substituent rotation and imino nitrogen inversion has been identified for 2 (R = t-Bu, 2,6-Me2C6H3), the interpretation of which is supported by the X-ray crystal structure determination of 2 (R = t-Bu).  相似文献   

14.
Treatment of [W(CO)(MeC2Me)2(-C5H5)][PF6] with ONMe3 in acetonitrile yields [W(NCMe)(MeC2Me)2(-C5H5)][PF6] which undergoes irreversible reduction at a Pt electrode in THF. Sodium amalgam reduction of [W(NCMe) (MeC2Me)2(-C5H5)][PF6] gives orange crystals of [W2(µ-,, 2, 2-C4Me4)2 (-C5H5)2] X-ray studies on which reveal pairwise alkyne coupling and a novel bis(metallacyclopentadiene) structure.Dedicated to Professor L. F. Dahl on the occasion of his 65th birthday.  相似文献   

15.
The metallation of the η5-C5H5(CO)2Fe-η15-C5H4Mn(CO)3 complex with BunLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph2PCl afforded the η5-Ph2PC5H4(CO)2Fe-η15-C5H4Mn(CO)3 complex. The reaction of the latter with η5-C5H5(CO)3WCl in the presence of Me3NO produced the trinuclear complex η5-C5H5Cl(CO)2W-η15-(Ph2P)C5H4(CO)2Fe-η15-C5H4Mn(CO)3. The structure of the latter complex was established by IR, UV, and 1H and 31P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl3 with three equivalents of LiC5H4(CO)2Fe-η15-C5H4Mn(CO)2PPh3 gave the hexanuclear complex MeSi[C5H4(CO)2Fe-η15-C5H4Mn(CO)2PPh3]3.  相似文献   

16.
《Polyhedron》1999,18(20):2583-2595
The reaction of the novel ferrocenyl Schiff base: [(η5-C5H5)Fe{(η5-C5H4)-CH=N-(C6H4-2-C6H5)}] (1) with Na2[PdCl4] and Na(CH3COO)·3H2O in a 1:1:1 molar ratio in methanol is reported. In this reaction two different di-μ-chloro-bridged cyclopalladated complexes: [Pd{[(η5-C5H3)-CH=N-(C6H4-2-C6H5)]Fe(η5-C5H5)}(μ-Cl)]2 (2a) and [Pd{[(C6H4-2-C6H4)-N=CH-(η5-C5H4)]Fe(η5-C5H5)}(μ-Cl)]2 (2b) can be formed depending on the experimental conditions. Compounds 2a and 2b, which differ in the nature of the metallated carbon atom (Csp2,ferrocene or Csp2,biphenyl, respectively), undergo cleavage of the ‘Pd(μ-Cl)2Pd’ bridges in the presence of thallium (I) acetylacetonate, deuterated pyridine or triphenylphosphine giving the monomeric derivatives: [Pd(CN)(acac)] (3a, 3b) and [Pd(CN)Cl(L)] {with L=py- d5(4a, 4b), PPh3(5a, 5b)}. The reactions of 2 with 1,2-bis(diphenylphosphino)ethane (dppe) reveal that the two isomers (2a and 2b) exhibit different reactivity versus dppe. These results have been interpreted on the basis of steric effects.  相似文献   

17.
Abstract

Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently1. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η5-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η5-C5Me5) (η5-C2 tBu2P3]. In the ruthenium complex [Fe(η5-C5Me5)(η5-C2 tBu2P3) Ru3(CO)9] 2 two adjacent phosphorus atoms of the η5-C2 tBu2P3 ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(CO)2]2 3 represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres.  相似文献   

18.
It is shown that (1,2,7-η3-2-Me-benzyl)(η5-C5H5)Mo(CO)2 exits in solution as one isomer which is fluxional, probably via (7-η1-2-Me-benzyl)((η5-C5H5)Mo(CO)2, with ΔG370 = 23.6 ± 1.0 kcal mol−1. In contrast, (1,2,7-η3-3-Me-benzyl)(η5-C5H5)Mo(CO)2 exits as two isomers at −20°C, which undergo interconversion at room temperature with ΔG 15.7 kcal mol−1. This dynamic process is an allyl rotation. It is probable that there is also a low energy [1,5]-sigmatropic shift.  相似文献   

19.
《Solid State Sciences》2001,3(7):783-788
The synthesis and structural characterization of the complex [Ru(η6-C6H6)(η6-C6H4(CH3)COOCH3)] [BF4]2 (2) and of its precursor [Ru(η6-C6H4(CH3)COOCH3)Cl2]2 (1) are reported. Compound (2) has been characterized in two polymorphic modifications (2a and 2b) and the molecular organization in the solid state has been investigated. The complex [Ru(η5-C5H5)(η6-C6H5OH)][PF6] (3) has also been investigated; it has been shown to possess a disorder similar to that observed in the high temperature phase of related systems such as [Ru(η5-C5H5)(η6-C6H6)][PF6].  相似文献   

20.
《Polyhedron》1986,5(3):921-923
The treatment of (η-C5H5)OMo(μ-O)2MoO(η-C5H5) with excess phenylisocyanate at reflux in tetrahydrofuran yields the arylimido-substituted complex (η-C5H5)(NPh)Mo(η-NPh)2Mo(NPh)(η-C5H5), which has been characterized by elemental analysis, and mass, IR and 1H NMR spectra.  相似文献   

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