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51.
Skabitskii I. V. Sakharov S. G. Pasynskii A. A. Eshmakov R. S. 《Russian Journal of Coordination Chemistry》2019,45(8):539-547
Russian Journal of Coordination Chemistry - The rhenium complexes TpReOCl(StBu) (I), TpReO(StBu)2 (II), and TpReO(SnC3H7)2 (III) are synthesized using two methods by analogy to the known thiophenyl... 相似文献
52.
Yu.V. Skripkin O.G. Volkov A.A. Pasynskii A.S. Antsyshkina L.M. Dikareva V.N. Ostrikova M.A. Porai-Koshits S.L. Davydova S.G. Sakharov 《Journal of organometallic chemistry》1984,263(3):345-357
Treatment of niobocene carbonylhydride, Cp2Nb(CO)H (I), with PhnSnCl4?n and Et2SnCl2 in THF in the presence of Et3N leads to the respective heteronuclear complexes Cp2Nb(CO)SnRnCl3?n (R = Ph, n = 3 ÷ 1 (II–IV), R = Et, n = 2 (V)). Treatment of II with HCl in ether gives Cp2Nb(CO)SnCl3 (VI). Complex VI and its analog (MeC5H4)2Nb(CO)SnCl3 (VIII) were prepared by an alternative synthesis using direct reaction of I or (MeC5H4)2Nb(CO)H with an equimolar quantity of SnCl4 in THF in the presence of Et3N. Complex VI is also generated by insertion of SnCl2 into the NbCl bond in Cp2Nb(CO)Cl (VII). X-Ray analysis of complexes II and VIII was performed: for II, space group P21/n, a = 10.1021(21), b = 17.4633(32), c= 14.2473(29) Å, β = 95.578(16)°, Z = 4; for VIII, space group. P21/n, a= 8.9369(15), b = 13.3589(12), c = 13.9292(20) Å, β = 99.490(14)°, Z = 4. The NbSn bond in VIII (2.764(9) Å) is shorter than that in II (2.825(2) Å). In both cases the NbSn bond is significantly shorter than the sum of Nb and Sn covalent radii (1.66 + 1.40 = 3.06 Å). It is probably partly multiple in character owing to an additional interaction of the lone electron pair of the NbIII ion (d2 configuration) with the antibonding Sn orbitals. The PMR spectra of II–VI exhibit two satellites of the singlet of C5H5 protons because of HSn117 and HSn119 spin-spin coupling (SSC). The SSC constant correlates with the number of electronegative chlorine atoms on the Sn atom. 相似文献
53.
A. A. Pasynskii A. N. Il’in S. S. Shapovalov Yu. V. Torubaev 《Russian Journal of Inorganic Chemistry》2007,52(6):875-878
New chromium and tungsten pentacarbonyl complexes with 5-mercapto-2,3-diphenyltetrazole coordinated through the sulfur atom (Cr-S, 2.4655(7) Å; W-S, 2.5755(13) Å) were synthesized and structurally characterized. 相似文献
54.
A.A. Pasynskii Yu.V. Skripkin V.T. Kalinnikov M.A. Porai-Koshits A.S. Antsyshkina G.G. Sadikov V.N. Ostrikova 《Journal of organometallic chemistry》1980,201(1):269-281
CpFe(CO)2CH3 reacts with Cp2NbH made from Cp2NbBH4 and Et3N to give Cp2e (III). As shown by X-ray diffraction, III contains the Cp2NbH sandwich fragment with a 46.8° angle between the rings linked with the dicarbonyliron moiety by the NbFe bond (2.968 Å), observed for the first time, and a cyclopentadienyl bridge C5H4, involving the NbC. σ-bond (2.189 Å) and C5H4Fe π-bond (2.085 Å). A probable reaction scheme leading to III and general patterns of formation of other heterobinuclear derivatives of sandwich complexes Cp2MLM′(L′)n are discussed. The importance of steric effects due to nonbonded interligand interactions between the M′(L′)n fragment and the sandwich system is emphasized. Increase of steric strain in the binuclear system facilitates its unusual transformations. 相似文献
55.
56.
57.
A.A. Pasynskii I.L. Eremenko B. Orazsakhatov Yu.V. Rakitin V.M. Novotortsev O.G. Ellert V.T. Kalinnikov G.G. Aleksandrov Yu.T. Struchkov 《Journal of organometallic chemistry》1981,210(3):385-394
The photochemical reaction between the antiferromagnetic complex (C5H5-CrSCMe3)2S (I) (containing a CrCr bond 2.689 Å long) and Fe(CO)5 results in the elimination of two carbonyl groups and one tert-butyl radical to give (C5H5Cr)2(μ2-SCMe3)(μ3-S)2 · Fe(CO)3 (III). As determined by X-ray diffraction, III contains a CrCr bond of almost the same length as in I (2.707 Å), together with one thiolate and two sulphide bridges. The latter are also linked with the Fe atom of the Fe(CO)3 moiety (average FeS bond length 2.300 Å). Fe also forms a direct bond, 2.726 Å long, with one of the Cr atoms, whereas its distance from the other Cr atom (3.110 Å) is characteristic for non-bonded interactions. Complex III is antiferromagnetic, the exchange parameter, ?2J, values for CrCr, Cr(1)Fe and Cr(2)…Fe are 380, 2600 and 170 cm?1, respectively. The magnetic properties of III are discussed in terms of the “exchange channel model”. The contributions from indirect interactions through bridging ligands are shown to be insignificant compared with direct exchange involving metalmetal bonds. The effects of steric factors and of the nature of the M(CO)n fragments on the chemical transformations of (C5H5CrSCMe3)2S · M(CO)n are discussed. 相似文献
58.
A.A. Pasynskii I.L. Eremenko O.G. Ellert V.M. Novotortsev Yu.V. Rakitin V.T. Kalinnikov V.E. Shklover Yu.T. Struchkov 《Journal of organometallic chemistry》1982,234(3):315-322
By heating the mixture of solutions of (CpCrSCMe3)2S (I) in benzene and [CpNi(CO)]2 in pentane followed by chromatography on alumina, dark cherry-red needles of the heteronuclear cluster (Cp4Cr2Ni2)(μ3-S)2(μ4-S) (II) were obtained, whose structure was established on the basis of a complete X-ray analysis. The crystals are rhombic, spatial group Pbca; a = 12.07(1), b = 18.50(2), c = 17.36(1) Å, Z = 8. The metallic skeleton of II has the “butterfly” or “metal-chain” structure with a direct CrCr bond (2.62(1) Å) and inequivalent CrNi bonds, 2.86(1) and 2.64(1) Å, while the Ni·Ni distance is nonbonding (4.34(1) Å). The NiCr2 triangle planes produce a dihedral angle of 127°. The two μ3-bridged sulfur atoms locate under these triangles whereas the third sulfur atom is μ4-bridging coordinating all four metal atoms in the cluster with mean NiS and CrS distances of 2.29(1) and 2.25(1) Å, respectively. The Ni2S3 group is planar and almost perpendicular to the CrCr axis. Complex II is anti-ferromagnetic and its exchange parameter — 2J (418 cm-1) is close to that found for the initial binuclear complex I (— 2J = 430 cm-1 with a CrCr bond length of 2.689(8) Å). The role of the Ni coordination number in the generation of II is discussed. 相似文献
59.
60.
Yu. V. Torubaev A. A. Pasynskii P. Mathur 《Russian Journal of Coordination Chemistry》2009,35(11):807-811
Reactions of Ru3(CO)12 with PhTeBr3 and of Re(CO)5Cl with PhTeI in benzene give the stable complexes (CO)2RuBr2(PhTeBr)2 (I) and (CO)3Re(PhTeI)3(μ3-I) (II) containing two and three ligands PhTeX (X = Br or I), respectively. The bonds between these ligands and the central metal
atom are fairly shortened (on average, Ru-Te, 2.608 ?; Re-Te, 2.7554(12)-2.7634(13) ?). The Te-X bonds in the ligands PhTeBr
(2.5163(5) ?) and PhTeI (2.7893(15) ?) are not lengthened appreciably. In complex II, the iodide anion is not coordinated by rhenium, yet being attached through weak secondary bonds to three Te atoms of the
three ligands PhTeI. 相似文献