共查询到20条相似文献,搜索用时 46 毫秒
1.
P. A. Abramov M. N. Sokolov I. V. Mirzaeva N. K. Moroz 《Russian Journal of Coordination Chemistry》2013,39(5):379-387
Reactions of [CpRhCl2]2 (Cp = η5-C5Me5 (Cp*), η5-C5Me4Et (Cp′), η5-C5H3 t Bu2(Cp″)) with in situ generated H2Se give triangular [Cp3Rh3Se2]2+ clusters. These clusters were isolated as PF6 salts and characterized with ESI-MS, 77Se, 1H NMR and DFT calculations. [Cp3Rh3Se2] undergoes two reversible two-electron reduction steps. Quantum-chemical calculations reveal non-trivial bonding situation in the cluster core and changes in the hapticity of the Cp* ligand upon reduction. Crystal structure of [Cp 3 * Rh3Se2][Re2(μ-Cl)3(CO)6]Cl · 3.3H2O has been determined. 相似文献
2.
3.
4.
The reaction of [Cp*MoCl(4)] with an excess of LiBH(4), followed by thermolysis with tellurium powder in toluene, afforded a tricapped cubane cluster, [(Cp*Mo)(4)B(4)H(4)(μ(4)-BH)(3)] (1), which represents an unprecedented metal-rich metallaborane cluster with a cubane core containing 58 cluster valence electrons (cve) and three metal-metal bonds. 相似文献
5.
《Journal of organometallic chemistry》1994,476(1):C1-C5
3,4-Bis[pentamethylcyclopentadienyl]tricyclo-[3.1.0.02,6] hexaphosphane 1 reacts with Cr(CO)5thf or W(CO)5thf to give the zwitterionic chromium complex 1,9,10-tris(pentacarbonylchromium)−3,4,5,6,11-pentamethyl-7-pentamethylcyclopentadienyl-3,4,5,6,11-pentacarba-penta-cyclo-[6.1. 1.1,8.13,6.O2,7.010,11 ]-4-en-7-ium-9-id-undeca-phosphane 2 and the analogous tungsten compound 3, respectively. The basic structures of 2 and 3 are similar to the cunean-moiety of the Hittorf-modification of phosphorus. 相似文献
6.
《Journal of organometallic chemistry》1991,410(1):C9-C12
The triisocyanide ligand CH3C(CH2NC)3, time, reacts with metal carbonyls M(CO)x (M = Cr, W, χ = 6; M = Fe, χ = 5) to give the triply metal carbonyl substituted complexes CH3C[CH2NCM(CO)x]3 (M = Cr, W, χ = 5; M = Fe, χ = 4). CH3C[CH2NCW(CO)5]3 was characterized by an X-ray structure determination. 相似文献
7.
《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
8.
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
9.
《Journal of organometallic chemistry》1986,299(3):377-381
Oxidative addition of XCN (X = Br, I) to Cp′Co(CO)L (L = CO, PPh3) leads to the formation of Cp′CoL(CN)X. The complexes C′pCoTCNE(L) do not react with XCN. 相似文献
10.
The substituted sandwich complex crystallizes in monoclinic space groupP21/m withZ=2. Twinning to the (001) direction with the special conditionc
*/4a
* = cos
* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l=2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged atR = 0.040,R
w
=0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of decamethylruthenocene. 相似文献
11.
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
12.
《Journal of organometallic chemistry》1986,303(2):C33-C37
The bis(sodium-metallates) Na2{Me2Si[(C5H4)M(CO)3]2} (4a: M = Mo, 4b, M = W), in which the metal centres are linked by their cyclopentadienyl ligands through a Me2Si unit are obtained by the reaction of Na2[(C5H4)2SiMe2] (2) with two moles M(CO)6 (3a: M = Mo; 3b: M = W). Treatment of 4a with Me2AsCl leads to the formation of the bis(metalloarsane) Me2Si[(C5H4(CO)3- MoAsMe2]2 (5), which is quarternized by MeI at the arsenic atoms to give the dicationic complex {Me2Si[(C5H4)(CO)3MoAsMe3]2}I2 (7). In reactions with the ylide Me3PCH2 cleavage of the MoAs bonds occurs, followed by transylidation to yield the bis(phosphonium metallate) [Me4P]2 {Me2Si[(C5H4)Mo- (CO)3]2} (10) and Me3PCHAsMe2 (9). From 4a, 4b and MeI the dinuclear methyl complexes Me2Si[(C5H4)(CO)3MMe]2 (6a: M=Mo; 6b: M=W) are obtained. 相似文献
13.
George MW Hall MB Portius P Renz AL Sun XZ Towrie M Yang X 《Dalton transactions (Cambridge, England : 2003)》2011,40(8):1751-1757
Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the rate of C-H activation of alkanes by Cp'Rh(CO) {Cp' = η(5)-C(5)H(5) or η(5)-C(5)Me(5); alkane = cyclopentane, cyclohexane and neopentane (Cp only)} in solution at room temperature and allowed the determination of how the change in rate of oxidative cleavage varies between complexes and alkanes. Density functional theory calculations on these complexes, transition states, and intermediates provide insight into the mechanism and barriers observed in the experimental results. Unlike our previous study of the linear alkanes, where activation occurred at the primary C-H bonds with a rate governed by a balance between these activations and hopping along the chain, the rate of C-H activation in cyclic alkanes is controlled mainly by the strength of the alkane binding. Although the reaction of CpRh(CO)(neopentane) to form CpRh(CO)(neopentyl)H clearly occurs at a primary C-H bond, the rate is much slower than the corresponding reactions with cyclic alkanes because of steric factors with this bulky alkane. 相似文献
14.
The reaction of 1-phenacylimidazole with W(CO)6 in a 1:1 molar ratio under irra- diation with a high-pressure Hg lamp mainly yielded the title compound (C29H26N4O7W, Mr = 726.39), which is of orthorhombic, space group Pbca with a = 27.665(4), b = 7.7807(12), c = 27.803(4) (A), V = 5984.8(16) (A)3, Z = 8, Dc = 1.612 g/cm3, λ(MoKα) = 0.71073 (A), μ = .3.911 mm-1, F(000) = 2864, R = 0.0583 and wR = 0.1502 for 3356 observed reflections (I > 2σ(I)). The crystal structural analysis indicates that in the coordination geometry of tungsten, 1-phenacylimidazole acts as a monodentate ligand and two imidazole ligands locate in a cis-position. 相似文献
15.
16.
17.
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
18.
《Journal of organometallic chemistry》1987,327(2):C51-C56
When solutions of (η-C5H5)2Rh2(CO)(CF3C2CF3) and [Rh(CO)2Cl]2 in hexane are mixed and left at room temperature, black crystals of the condensation product (η-C5H5)2Rh4(CO)4Cl2(CF3C2CF3) are deposited. X-ray structure determination shows that one rhodium atom of the [Rh(CO)2Cl]2 dimer has added to the RhRh bond of (η-C5H5)2Rh2(CO)(CF3C2CF3) to form a triangular Rh3 cluster. This is capped on one side by a semi-face bridging carbonyl and on the other by a μ3η2 bound alkyne. Variable temperature NMR data reveal that two isomers of the complex co-exist in solution and that they rapidly interconvert at room temperature. In similar reactions between (η-C5H5)2Rh2(CO)(CF3C2CF3) and Pt(COD)2 in hexane at room temperature, there is loss of cyclooctadine and the formation of two cluster products. One is formulated as (η-C5H5)2Rh2Pt(COD)(CF3C2CF3) and the other as (η-C5H5)4Rh4Pt(CO)2(CF3C2CF3)2. Determination of the X-ray crystal structure of the latter establishes that the Pt is a common apex for two linked Rh2Pt triangles. Within each Rh2Pt unit, a semi-bridging carbonyl spans one Rh-Rh edge, and the hexaluorobut-2-yne occupies a μ3η2 face bridging position. 相似文献
19.
《Journal of organometallic chemistry》1986,299(2):213-221
We report the synthesis and characterisation of binuclear η5-pentamethylcyclopentadienylrhenium complexes, [(η5-C5Me5)Re(CO)2]2(μ-E) (E = S (2), Se (3), Te (4)), containing a chalcogen bridge in addition to a ReRe bond. According to the X-ray structural analysis, 3 possesses approximately C2 molecular symmetry; the C5Me5 ring ligands occupy trans positions with respect to the central Re2Se unit [d(ReRe) 3.032(1) Å, ∢ ReSeRe 74.9(1)°]. As expected, the complexes of the now complete series [CpRe(CO)2]2(μ-E) (E = O (1), S (2), Se (3), Te (4)) show a high degree of similarity in their corresponding mass, IR, 1H and 13C NMR spectra. 相似文献
20.
A. A. Pasynskii I. V. Skabitskii S. S. Shapovalov A. R. Galustyan Yu. V. Torubaev Zh. V. Dobrokhotova V. A. Grinberg E. V. Mutseneck A. R. Kudinov 《Russian Chemical Bulletin》2007,56(9):1731-1735
The reaction of Cb*Co(CO)2I (1) (Cb* is tetramethylcyclobutadiene) with sodium phenyltelluride afforded the mononuclesar complex Cb*Co(CO)2TePh (2). The reaction of the latter with W(CO)5(THF) produced the Cb*Co(CO)2TePh[W(CO)5] compound (4). The reaction of 1 with the Cp2Cr2(SCMe3)2S complex gave the heterometallic cluster Cb*Co(μ3-S)2Cr2Cp2 (μ-SCMe3) (5). Complexes 2, 4, and 5 are diamagnetic. Their structures were determined by X-ray diffraction. Complex 2 contains the Co-Te bond (2.585(1) Å); complex 4, the Co-Te (2.558(8) Å) and W-Te (2.8467(6) Å) bonds. Complex 5 has the stable triangular sulfide-and tert-butylmercaptide-bridged core Cr2Co (Cr-Cr and Cr-Co bond lengths are 2.626(2) and 2.673(2) Å, respectively) with Cp ligands at the chromium atoms and a Cb* ligand at the cobalt atom. Complex 5 was characterized by cyclic voltammetry. The thermolysis of complex 4 was studied. 相似文献