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1.
Dielmann F Schindler A Scheuermayer S Bai J Merkle R Zabel M Virovets AV Peresypkina EV Brunklaus G Eckert H Scheer M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(4):1168-1179
Slow diffusion reactions of the pentaphosphaferrocene [Cp*Fe(η(5)-P(5))] (Cp*=η(5)-C(5)Me(5) (1)) with CuX (X=Cl, Br, I) in different stoichiometric ratios and solvent mixtures result in the formation of one- and two-dimensional polymeric compounds 2-6 with molecular formula [{Cu(μ-X)}{Cp*Fe(μ(3),η(5):η(1):η(1)-P(5))}](n) (X=Cl (2a), I (2'c)), [{Cu(μ-I)}{Cp*Fe(μ(3),η(5):η(1):η(1)-P(5))}](n) (3), [{CuX}{Cp*Fe(μ(4),η(5):η(1):η(1):η(1)-P(5))}](n) (X=Cl (4a), Br (4b), I (4c), Br (4'b), I (4'c)), [{Cu(3)(μ-I)(2)(μ(3)-I)}{Cp*Fe(μ(5),η(5):η(1):η(1):η(1):η(1)-P(5))}](n) (5) and [{Cu(4)(μ-X)(4)(CH(3)CN)}{Cp*Fe(μ(7),η(5):η(2):η(1):η(1):η(1):η(1):η(1)-P(5))}](n) (X=Cl (6a), Br (6b)), respectively. The polymeric compounds have been characterised by single-crystal X-ray diffraction analyses and, for selected examples, by magic angle spinning (MAS) NMR spectroscopy. The solid-state structures demonstrate the versatile coordination modes of the cyclo-P(5) ligand of 1, extending from two to five coordinating phosphorus atoms in either σ or σ-and-π fashion. In compounds 2a, 2'c and 3, two phosphorus atoms of 1 coordinate to copper atoms in a 1,2 coordination mode (2a, 2'c) and an unprecedented 1,3 coordination mode (3) to form one-dimensional polymers. Compounds 4a-c, 4'b, 4'c and 5 represent two-dimensional coordination polymers. In compounds 4, three phosphorus atoms coordinate to copper atoms in a 1,2,4 coordination mode, whereas in 5 the cyclo-P(5) ligand binds in an unprecedented 1,2,3,4 coordination mode. The crystal structures of 6a,b display a tilted tube, in which all P atoms of the cyclo-P(5) ligand are coordinated to copper atoms in σ- and π-bonding modes. 相似文献
2.
Rainer Bartsch Christian Müller Axel Fischer Peter G. Jones 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
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
3.
《Journal of organometallic chemistry》1992,430(1):C10-C14
The lone-pair electrons of one of the two directly bonded phosphorus atoms of the P3C2tBu2 ring in the penta- or hexaphosphaferrocene complexes [Fe(η5-P3C2tBu2)(η5-P3C2tBu3)] and [Fe(η5P3 C2tBu2)2] can ligate to other metal centres to afford novel bi- and tetrametallic complexes, whose structures have been elucidated by NMR and single crystal X-ray crystallographic studies. 相似文献
4.
5.
《Journal of organometallic chemistry》1986,316(3):315-318
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
6.
The reaction of [(η-C7H7)Mo(MeCN)3)]BF4 with (η-C5Me5)Fe(η-P5) afforded the new 30-electron triple-decker complex [(η-C7H7)Mo(μ-η:η-P5)Fe(η-C5Me5)]BF4. Studies of the temperature dependence of the1H NMR spectra demonstrated that the resulting compound contains a fluxional cyclohepatrienyl ligand.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1374–1376, July, 1999. 相似文献
7.
《Journal of organometallic chemistry》1998,571(2):289-295
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
8.
9.
《Journal of organometallic chemistry》1988,353(2):C23-C26
Mild, reductive carbonylation of (C5Me5)TaCl4 in the presence of trimethylphosphine gives (C5Me5)Ta(CO)4 in 47% yield. The intermediate (C5Me5)TaCl2- (CO)2(PMe3) has been isolated from the reaction of (C5Me5)TaCl2(PMe3)2 with carbon monoxide and its crystal structure determined (space group P212121). 相似文献
10.
C-H activation of arenes and heteroarenes has been achieved by a hydrogen rich tantalaborane cluster [(Cp*Ta)(2)B(5)H(11)] that leads to the formation of C-H functionalized products. Furthermore, we examined the reaction of substituted thiophene and pyrrole derivatives with tantalaborane which provided a convenient and efficient route to regio-defined C-H functionalized heteroarenes. 相似文献
11.
Dr. Claudia Heinl Dr. Eugenia Peresypkina Dr. Gábor Balázs Dr. Eric Mädl Dr. Alexander V. Virovets Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(27):7542-7548
The so far missing parent compound of the large family of pentaphosphaferrocenes [CpFe(η5-P5)] ( 1 b ) was synthesized by the thermolysis of [CpFe(CO)2]2 with P4 using the very high-boiling solvent diisopropylbenzene. It was comprehensively characterized by, inter alia, NMR spectroscopy, single crystal X-ray structure analysis, cyclic voltammetry and DFT computations. Moreover, its coordination behavior towards CuI halides was explored, revealing the unprecedented 2D polymeric networks [{CpFe(η5:1:1:1:1-P5)}Cu2(μ-X)2]n ( 2 a : X=Cl, 2 b : X=Br) and [{CpFe(η5:1:1-P5)}Cu(μ-I)]n ( 3 ) and even the first cyclo-P5-containing 3D coordination polymer [{CpFe(η5:1:1-P5)}Cu(μ-I)]n ( 4 ). The sandwich complex 1 b can also be incorporated in nano-sized supramolecules based on [Cp*Fe(η5-P5)] ( 1 a ) and CuX (X=Cl, Br, I): [CpFe(η5-P5)]@[{Cp*Fe(η5-P5)}12(CuX)20-n] ( 5 a : X=Cl, n=2.4; 5 b : X=Br, n=2.4; 5 c : X=I, n=0.95). Thereby, the formation of the CuI-containing fullerene-like sphere 5 c is found for the first time. 相似文献
12.
《Journal of organometallic chemistry》1986,316(3):325-333
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
13.
Anna Garbagnati Dr. Michael Seidl Dr. Gábor Balázs Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200669
The oxidation of [(Cp*Mo)2(μ,η6:η6-P6)] ( 1 ) with halogens or halogen sources was investigated. The iodination afforded the ionic complexes [(Cp*Mo)2(μ,η3:η3-P3)(μ,η1:η1:η1:η1-P3I3)][X] (X=I3−, I−) ( 2 ) and [(Cp*Mo)2(μ,η4:η4-P4)(μ-PI2)][I3] ( 3 ), while the reaction with PBr5 led to the complexes [(Cp*Mo)2(μ,η3:η3-P3)(μ-Br)2][Cp*MoBr4] ( 4 ) [(Cp*MoBr)2(μ,η3:η3-P3)(μ,η1-P2Br3)] ( 5 ) and [(Cp*Mo)2(μ-PBr2)(μ-PHBr)(μ-Br)2] ( 6 ). The reaction of 1 with the far stronger oxidizing agent PCl5 was followed via time- and temperature-dependent 31P{1H} NMR spectroscopy. One of the first intermediates detected at 193 K was [(Cp*Mo)2(μ,η3:η3-P3)(μ-PCl2)2][PCl6] ( 8 ) which rearranges upon warming to [(Cp*Mo)2(μ-PCl2)2(μ-Cl)2] ( 9 ), [(Cp*MoCl)2(μ,η3:η3-P3)(μ-PCl2)] ( 10 ) and [(Cp*Mo)2(μ,η4:η4-P4)(μ-PCl2)][Cp*MoCl4] ( 11 ), which could be isolated at room temperature. All complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy and their electronic structures were elucidated by DFT calculations. 相似文献
14.
Sh. G. Mkoyan Z. G. Aliev L. O. Atovmyan P. V. Ivchenko 《Russian Chemical Bulletin》1995,44(2):296-299
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
15.
16.
Neil G. Connelly Thomas Escher Antonio J. Martin Bernhard Metz A. Guy Orpen 《Journal of Cluster Science》1995,6(1):125-134
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
17.
《Comptes Rendus Chimie》2002,5(4):319-324
The ligand substitution by diphosphine L–L on (η5-C5H5)Fe(CO)2I usually results in the chelated 〚(η5-C5H5)Fe(CO)(η2-L–L)+〛〚I–〛 product exclusively. One could suppress the chelated complexes and selectively prepare the bridged 〚{(η5-C5H5)Fe(CO)2}2(μ-L–L)2+〛 complexes by application of the electron-transfer chain catalysis with a chemical initiation. Introducing a catalytic amount of reductant at low temperature to the mixture of 2:1 (η5-C5H5)Fe(CO)2I/L–L in THF selectively produces the bridged complexes in 78–93% isolated yields where L–L is Ph2P(CH2)nPPh2, n = 1–4, or (η5-C5H4PPh2)2Fe. 相似文献
18.
Pandey KK 《The journal of physical chemistry. A》2011,115(30):8578-8585
Density functional theory calculations have been performed for the dimethylgallyl complexes of iron, ruthenium, and osmium [(η(5)-C(5)H(5))(L)(2)M(GaMe(2)] (M = Fe, Ru, Os; L = CO, PMe(3)) at the DFT/BP86/TZ2P/ZORA level of theory. The calculated geometry of the iron complex [(η(5)-C(5)H(5))(CO)(2)Fe(GaMe(2))] is in excellent agreement with structurally characterized complex [(η(5)-C(5)H(5))(CO)(2)Fe(Ga(t)Bu(2))]. The Pauling bond order of the optimized structures shows that the M-Ga bonds in these complexes are nearly M-Ga single bond. Upon going from M = Fe to M = Os, the calculated M-Ga bond distance increases, while on substitution of the CO ligand by PMe(3), the calculated M-Ga bond distances decrease. The π-bonding component of the total orbital contribution is significantly smaller than that of σ-bonding. Thus, in these complexes the GaX(2) ligand behaves predominantly as a σ-donor. The contributions of the electrostatic interaction terms ΔE(elstat) are significantly smaller in all gallyl complexes than the covalent bonding ΔE(orb) term. The absolute values of the ΔE(Pauli), ΔE(int), and ΔE(elstat) contributions to the M-Ga bonds increases in both sets of complexes via the order Fe < Ru < Os. The Ga-C(CO) and Ga-P bond distances are smaller than the sum of van der Waal radii and, thus, suggest the presence of weak intermolecular Ga-C(CO) and Ga-P interactions. 相似文献
19.
《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
20.
《Journal of organometallic chemistry》1994,464(1):47-54
Isomeric pairs of silicon-germanium compounds containing a SiGe 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 FeSiGe fragmentation occurs predominantly via SiGe bond cleavage with formation of ions containing the silylene ligand [FeSiR2]+. Complexes with the FeGeSi backbone undergo preferential scission of the FeGe bond, illustrating the general bond strength trend FeSi > SiGe. Upon direct cleavage of the SiGe 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 SiGe bond. 相似文献