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1.
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
2.
Braunschweig H Fuss M Kupfer T Radacki K 《Journal of the American Chemical Society》2011,133(15):5780-5783
Selective dimetalation of a sandwich complex featuring the cyclooctatetraene ligand has been accomplished for the first time. The isolation of the dilithiated species 1 subsequently enabled the isolation of a paramagnetic [2]stannatitanoarenophane (2) via salt elimination reaction. Chemical oxidation resulted in the formation of a rare example of a cationic ansa-complex (3). 相似文献
3.
Paul R. Raithby Jack Lewis Catherine A. Morewood M. Carmen Ramirez de Arellano Gregory P. Shields 《Journal of Cluster Science》2006,17(1):13-26
Thermolysis of [Ru3(CO)12] in cyclohexene for 24 h affords the complexes [Ru(CO)3(η4-C6H8)] (1), [Ru3H2(CO)9(μ2-η1:η2:η1-C6H8)] (2), [Ru4(CO)12(μ4-C6H8)] (3) [Ru4(CO)9(μ4-C6H8)(η6-C6H6)] (4a and 4b, two isomers) and [Ru5(CO)12(μ4-η2-C6H8)(η4-C6H8)] (5), where 1, 3, 4a and 4b have been previously characterised as products of the thermolysis of [Ru3(CO)12] with cyclohexa-1,3-diene. The molecular structures of the new clusters 2 and 5 were determined by single-crystal X-ray crystallography, showing that two conformational polymorphs of 5 exist in the solid state, differing in the orientation of the cyclohexa-1,3-diene ligand on a ruthenium vertex. 相似文献
4.
《Journal of organometallic chemistry》1987,330(3):415-428
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--C5H4CCo3(η5C5H5)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
5.
《Journal of organometallic chemistry》1986,299(3):341-345
The complex (η5-C5H5)Cr(CO)3Cp42 H5 has been made and its reactions with σ donor ligands L (L = (MeO)3P and (EtO)3P) and with SO2 studied. The alkyl phosphites give compounds of the composition (η5-C5H5)Cr(CO)2LC2H5, and sulfur dioxide gives the corresponding S-sulfinato (η5-C5H5)Cr(CO)3SO2C2H5. 相似文献
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7.
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
8.
《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
9.
《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
10.
《Journal of organometallic chemistry》1987,331(2):221-228
Irradiation at λ = 507 and 391 nm of [Mo2(η5-C5H5)2(CO)6] in a degassed tetrahydrofuran (THF) or THF-MeOH solution containing nitrite gives [Mo(η5-C5H5)2NO] and several oxo complexes including [{Mo(η5-C5H5)(O)2}2O] in good yields. The quantum yields for the disappearance of [Mo2(η5-C5H5)2(CO)6] in the reaction with NO2− depend on the nitrite concentration, thus suggesting participation of the metal-radical intermediate in the reduction of nitrite. Reactions of [Mo2(η5-C5H5)2(CO)4] with nitrite or nitrate in the dark give the same nitrosyl and oxo complexes as above. An oxygen atom in nitrite or nitrate is mainly transferred onto the molybdenum atom both in the photochemical and the dark reactions. 相似文献
11.
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
12.
Olga Torres James A. Calladine Simon B. Duckett Michael W. George Robin N. Perutz 《Chemical science》2015,6(1):418-424
Irradiation of CpMn(CO)3 in liquid ethane at 135 K at 355 nm yields a photoproduct that exhibits ν(CO) bands in the IR spectrum shifted to low wavenumber with respect to CpMn(CO)3 that are indicative of a Mn(i) dicarbonyl. Parallel experiments employing in situ irradiation within an NMR probe (133 K, 355 nm photolysis) reveal the 1H NMR signals of this product and confirm its formulation as the σ-ethane complex CpMn(CO)2(η2-C1–H-ethane). The resonance of its coordinated C–H group is observed at δ –5.84 and decays with lifetime of ca. 360 s. Analogous photolysis experiments in isopentane solution with IR detection produce CpMn(CO)2(η2-C–H-isopentane) with similar IR bands to those of CpMn(CO)2(η2-C–H-ethane). 1H NMR spectra of the same species were obtained by irradiation of CpMn(CO)3 in a 60 : 40 mixture of propane and isopentane; three isomers of CpMn(CO)2(η2-C–H-isopentane) were detected with coordination of manganese at the two inequivalent methyl positions and at the methylene group, respectively. The lifetimes of these isomers are ca. 380 ± 20 s at 135 K and do not vary significantly from each other. These σ-complexes of manganese are far more reactive than those of related CpRe(CO)2(alkane) complexes which are stable in solution at 170–180 K. The room temperature lifetimes of CpMn(CO)2(η2-C–H-ethane) and CpMn(CO)2(η2-C–H-isopentane), as determined by TRIR spectroscopy, are 2.0 ± 0.1 and 28 ± 1 μs, respectively. 相似文献
13.
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.
《Journal of organometallic chemistry》1989,369(2):C21-C22
The salts [Fe2η5,η5-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
17.
《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
18.
Loginov D. A. Starikova Z. A. Petrovskii P. V. Kudinov A. R. 《Russian Chemical Bulletin》2010,59(3):654-656
The bromide complex [(η-C5H5BMe)RhBr2]2 (1) was synthesized by the reaction of the cyclooctadiene derivative (η-C5H5BMe)Rh(1,5-C8H12) with Br2. The reaction of compound 1 with Tl[Tl(η-7,8-C2B9H11)] gave (boratabenzene)rhodacarborane (η-7,8-C2B9H11)Rh-(η-C5H5BMe) (2). The structure of compound 2 was determined by X-ray diffraction 相似文献
19.
Yu. K. Gun'ko V. K. Bel'skii G. L. Soloveichik B. M. Bulychev 《Russian Chemical Bulletin》1993,42(6):1086-1089
X-ray structural analysis of a samarium triscyclopentadienyl complex, Cp3Sm·OC4H8 (1), and a samarium ionic salt, [Li(Et2O)2][Cp3Sm(-Cl)SmCp3] (2), was carried out. In both compounds coordination saturation is achieved by coordination of the THF molecule (in1) or the Cl– anion (in2) to the monomeric fragment Cp3Sm. An unusual coordination of the Li+ cation was observed in complex2: it is bound to one of the 5-type cyclopentadienyl rings in addition to two ether molecules.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1129–1132, June, 1993. 相似文献
20.
《Journal of organometallic chemistry》1987,326(1):C29-C32
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