共查询到20条相似文献,搜索用时 15 毫秒
1.
Zhang Yongqiang Wang Baiquan Xu Shansheng Zhou Xiuzhong 《Transition Metal Chemistry》1999,24(5):610-614
A series of bridged diruthenium complexes (E)[(5-C5H4)Ru(CO)]2(-CO)2 (E = Me2Ge (2); Me2SiOSiMe2 (3); Me2SiOSiMe2OSiMe2 (4)) has been prepared by reacting Ru3(CO)12 with Cp2E in refluxing heptane. The molecular structures of (2) and (4) have been determined by X-ray diffraction. 相似文献
2.
A. Z. Voskoboinikov E. B. Chuklanova I. N. Parshina A. K. Shestakova A. I. Gusev I. P. Beletskaya 《Russian Chemical Bulletin》1993,42(3):531-533
Cp*
2Lu(-Cl)2 (1) was isolated following the reaction of Cp*Na (Cp* = 1, 3-(Me3Si)2C5H3) with LuCl3 in THF and subsequent treatment with toluene at 80°C. An X-ray structural investigation of1 was performed (MoK
radiation, 2933 reflections,R = 0.020). The crystals are triclinic,a = 10.744(3) Å,b=11.821(2) Å, c=12.966(3) Å, a=71.54(1)°, =85.32(2)°, =74.83(1)°,Z = 2, space groupP-1. Two Lu atoms withdistorted tetrahedral coordination are linked by two chloride bridges with a mean Lu-Cl distance equal to 2.62 Å.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 568–570, March, 1993. 相似文献
3.
《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
4.
《Journal of organometallic chemistry》1987,327(2):C33-C36
(η5-C5Me5)(CO)2(PPh3)MoCHO (2) one of the few isolated neutral metal formyls, reacts with the electrophilic reagents (CF3COOH and CH3SO3F without disproportionation to give the secondary carbene complexes [(η5-C5Me5)(CO)2(PPh3)Mo(CHOE)]+ X− (E = H, X = CF3COO (4); E = Me, X = PF6 (5)). 相似文献
5.
《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
6.
《Journal of organometallic chemistry》1986,307(2):255-261
Synthetic routes to the cationic complexes [η5-C9H7Fe(CO)[2L]+, (L = CO, phosphine, phosphite, nitrile, pyridine) have been investigated. The most versatile method is oxidation of the dimer [η5-C9h7Fe(CO)2]2 with ferricinium ion. in the presence of the appropriate ligand. [η5-C9H7Fe(CO)3]+ is best prepared by oxidation of the dimer with Ph3CBF4. This tricarbonyl cation readily loses one CO group on reactiom with phosphines and P(OCH3). The acentonitrile ligand [η5-C9H7Fe(CO)2CH3CN]+ can also be replaced bny phosphines. Finally, reactions of η5-C9H7Fe(CO)2X, (X = Br, I) with phosphines also yield cationic products isolatedas PF6− salts. 相似文献
7.
《Journal of organometallic chemistry》1987,320(2):C19-C22
The complex [(η5-C5H5)Fe(CO)(PPh3)CH2CH3] is shown by 1H NMR spectroscopy and an X-ray crystal structure analysis to adopt a single conformation with the methyl group residing between the cyclopentadienyl and carbon monoxide ligands. 相似文献
8.
《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
9.
《Journal of organometallic chemistry》1988,339(3):339-343
The 13C {1H} NMR spectra of a series of complexes [(η5-C5H4Me)Fe(CO)(L)I] (L t-BuNC, P(OMe)3, PMe3, PMe2Ph, PMePh3, PPh3 and P(C6H11)3) have been recorded and the five cyclopentadienyl resonances assigned to ring carbon atoms by means of CH correlated spectra. It has been observed that the C atoms ortho to the ring methyl group (C(2) and C(5)) as well as the quaternary C atom are always coupled to the ligand P atom. A correlation between the chemical shift difference Δ(C(2) – C(5)) and the Tolman cone angle, θ, has also been established. 相似文献
10.
《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
11.
T. Yu. Orlova Yu. S. Nekrasov P. V. Petrovskii M. G. Ezernitskaya Z. A. Starikova O. L. Lependina 《Russian Chemical Bulletin》2008,57(1):63-67
The metallation of the η5-C5H5(CO)2Fe-η1,η5-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-η1,η5-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-η1,η5-(Ph2P)C5H4(CO)2Fe-η1,η5-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-η1,η5-C5H4Mn(CO)2PPh3 gave the hexanuclear complex MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3. 相似文献
12.
Density functional theory (DFT) calculations have been performed on the terminal dihalogallyl complexes of iron, ruthenium, and osmium (η(5)-C(5)H(5))(Me(3)P)(2)M(GaX(2)) (M = Fe, Ru, Os; X = Cl, Br, I) and (η(5)-C(5)H(5))(OC)(2)Fe(GaX(2)) (X = Cl, Br, I) at the BP86/TZ2P/ZORA level of theory. On the basis of analyses suggested by Pauling, the M-Ga bonds in all of the dihalogallyl complexes are shorter than M-Ga single bonds; moreover, on going from X = Cl to X = I, the optimized M-Ga bond distances are found to increase. From the perspective of covalent bonding, however, π-symmetry contributions are, in all complexes, significantly smaller than the corresponding σ-bonding contribution, representing only 4-10% of the total orbital interaction. Thus, in these GaX(2) complexes, the gallyl ligand behaves predominantly as a σ donor, and the short M-Ga bond lengths can be attributed to high gallium s-orbital character in the M-Ga σ-bonding orbitals. The natural population analysis (NPA) charge distributions indicate that the group 8 metal atom carries a negative charge (from -1.38 to -1.62) and the gallium atom carries a significant positive charge in all cases (from +0.76 to +1.18). Moreover, the contributions of the electrostatic interaction terms (ΔE(elstat)) are significantly larger in all gallyl complexes than the covalent bonding term (ΔE(orb)); thus, the M-Ga bonds have predominantly ionic character (60-72%). The magnitude of the charge separation is greatest for dichlorogallyl complexes (compared to the corresponding GaBr(2) and GaI(2) systems), leading to a larger attractive ΔE(elstat) term and to M-Ga bonds that are stronger and marginally shorter than in the dibromo and diiodo analogues. 相似文献
13.
《Polyhedron》1987,6(2):261-267
A new, high-yield method has been developed for the preparation of MO(CO)2I2(η2-dppm)(η1-dppm). The title compound was prepared by the reaction of [Et4N][Mo(CO)4I3] with dppm in benzene in 95% yield. It has been characterized by a single-crystal X-ray study. The crystallographic data are as follows: monoclinic, space group P21/n, a = 19.023(4) Å, b = 14.439(3) Å, c = 20.141(5) Å, β = 100.45(2)°, V = 5440(2) Å3 Z = 4. The geometry around the central metal atom could be considered as either a distortion from a capped octahedron with a carbonyl in a capping position or from a trigonal prism with the iodine capping a rectangular face. The solution behavior of Mo(CO)2I2(dppm)2 was examined with 31P NMR, which showed it to be fluxional. 相似文献
14.
《Journal of organometallic chemistry》1987,334(3):C39-C42
Thermolysis of cyclooctaselenadiazole (2) yields only selenium-containing products. Compound 2 reacts with CpCo sources to give [(η5-C5H5)CO]2(μ2η3,η2-C8H6Se), a fluxional compound whose structure has been determined by X-Ray crystallography. 相似文献
15.
《Journal of organometallic chemistry》1987,319(3):C45-C50
(η4-Tropone)Fe(CO)3 and (η4-isoprene)Fe(CO)3 form separable diastereoisomers on substitution of CO by (+)-(neomenthyl)PPh2. In the tropone complex, diastereoisomer interconversion occurs by a 1,3-metal shift. The absolute configuration of the isoprene complex has been determined crystallographically. 相似文献
16.
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
17.
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
18.
19.
20.
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