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1.
The electron density distribution and atomic displacements were analyzed based on the results of precision low-temperature X-ray diffraction studies of a series of isostructural (Pnma, Z = 4) mixed metallocenes (5-C5H5)M(5-C7H7) (M = Ti, V, or Cr) and (5-C5H5)Ti(8-C8H8). The barriers to rotation of the cyclic ligands were evaluated based on rms libration amplitudes. Analysis of the deformation electron density demonstrated that the character of the M--(-ligand) chemical bond depends substantially both on the nature of the metal atom and the size of the ligand. Lowering of the local symmetry of the (5-C5H5)M(5-C7H7) complexes to CS leads to distortion of the cylindrical symmetry of the electron density distribution observed in vanadocene (5-C5H5)2V and titanocene (5-C5H5)Ti(8-C8H8). 相似文献
2.
《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
3.
《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
4.
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
5.
《Journal of organometallic chemistry》1994,464(1):55-58
Reaction of 1/2 mole ratio of (η5-C5H5)SmCl2 ·3THF and NaCCCH2OCH2CHCH2 in THF solution resulted in the formation of (η5-C5H5)Sm·OC4H8; the complex crystallizes in monoclinic space group P21/n with unit cell constants a = 8.254(5), b = 24.63(1), c = 8.339(3) Å, β = 101.33(5)° and Dc = 1.67 g/cm3 for Z = 4. Refinement has led to a final R value of 0.041 based on 2106 independent observed reflections. The THF molecule is coordinated to the samarium atom at a SmO distance of 2.522(6) Å. The SmC(cyclopentadienyl) bond lengths range from 2.70(1) to 2.80(1) Å and average 2.742(1) Å. A comparison of some significant structural parameters along the isostructural series (η5-C5H5)3Ln·THF (LnLa, Pr, Nd, Gd, Dy, Lu and Sm) with the ionic radii of Ln3+ was made. 相似文献
6.
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
7.
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
8.
《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(C∧N)(acac)] (3a, 3b) and [Pd(C∧N)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
9.
《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
10.
《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
11.
(η^5-C5H5)(η^5-C5H4R)TiCl2类化合物的新合成方法 总被引:1,自引:0,他引:1
本文报道了取代环戊二烯基负离子与[(η~5-C_5H_5)TiCl_2]_2O反应生成(η~5-C_5H_5)(η~5-C_5H_4R)·TiCl_2的新方法。研究了取代环戊二烯基负离子的空间位阻和(η~5-C_5H_5)TiCl_3,[(η~5-C_5H_5)TiCl_2]_2O的结构以及反应温度对产物产率的影响。合成了七个新的(η~5-C_5H_5)(η~5-C_5H_4R)TiCl_2类型的化合物及七个相应的二氟化合物。 相似文献
12.
本文报道了取代环戊二烯基负离子与[(η^5-C5H5)TiCl2]2O反应生成(η^5-C5H5)(η^5-C5H4R).TiCl2的新方法. 研究了取代环戊二烯基负离子的空间位阻和(η^5-C5H5)TiCl3, [(η^5-C5H5)TiCl2]2O的结构以及反应温度对产物产率的影响. 合成了七个新的(η^5-C5H5)(η^5C5H4R)TiCl2类型的化合物及七个相应的二氟化合物。 相似文献
13.
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
14.
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
15.
《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
16.
《Comptes Rendus Chimie》2014,17(6):526-533
Thorocene [Th(Cot)2] (Cot = η8-C8H8) readily reacts with 2,2′-bipyridine to give [Th(Cot)2(κ2-bipy)], which has an unusual bent geometry. This compound is rapidly reduced by KC8 into the anionic derivative [(Th(Cot)2(κ2-bipy)]−. X-ray diffraction studies suggest the latter to be a Th(IV) compound with the bipyridyl radical anion. These complexes are rare examples of bent actinocene [An(Cot)2(L)]q− (q = 0, 1; An = actinide) and bipyridine-containing thorium species. 相似文献
17.
18.
Susanne Büschel Thomas Bannenberg Cristian G. Hrib Andreas Glöckner Peter G. Jones Matthias Tamm 《Journal of organometallic chemistry》2009,694(7-8):1244-1250
The reactions of [(η7-C7H7)Hf(η5-C5H5)] (1b) with the two-electron donor ligands tert-butyl isocyanide (tBuNC), 2,6-dimethylphenyl isocyanide (XyNC), 1,3,4,5-tetramethylimidazolin-2-ylidene (IMe) and trimethylphosphine (PMe3) are reported. The 1:1 complexes [(η7-C7H7)Hf(η5-C5H5)L] (2b, L = tBuNC; 3b, L = XyNC; 4b, L = IMe, 5b, L = PMe3) have been isolated in crystalline form, and their molecular structures have been determined by X-ray diffraction analyses. The stabilities of these hafnium complexes were probed via spectroscopic and theoretical methods, and the results were compared to those previously reported for the corresponding zirconium complexes derived from [(η7-C7H7)Zr(η5-C5H5)] (1a). The X-ray crystal structure of the PMe3 adduct [(η7-C7H7)Zr(η5-C5H5)(PMe3)] (5a) was also established. 相似文献
19.
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
20.
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