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1.
Van An Du Gregor N. Stipicic Maria Bendova Ulrich Schubert 《Monatshefte für Chemie / Chemical Monthly》2010,10(2):671-675
Abstract
Thermolysis of cis-Fe(CO)4(SiCl3)2 results in the formation of the novel compound Fe2(CO)6(μ2-SiCl2)3, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe2(CO)6(SiCl2)3, including CO dissociation and chlorine abstraction by a SiCl3 radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing. 相似文献2.
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
3.
室温下对苯二甲酸二丙炔醇酯分别与Co2CO8Mo2Cp2CO4和RuCo2CO11反应得到三个有机金属化合物C6H4pCO2CH2C2Hμ2Co2CO621、C6H4pCO2CH2C2H2RuCo2CO922和HC2CH2OCOC6H4pCO2CH2C2HμMo2Cp2CO43。研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2CO9>Co2CO6>Mo2CO4Cp2。化合物1的晶体衍射发现属三斜晶系空间群a=8.1392b=8.8083c=11.3433β=96.2606°V=773.443Z=1Dc=1.748g·cm-3R=0.0513wR=0.1266。 相似文献
4.
The cyclopentadienylchromium carbonyl thiocarbonyls Cp2Cr2(CS)2(CO)n (n = 4, 3, 2, 1) have been studied by density functional theory using the B3LYP and BP86 functionals. The lowest energy Cp2Cr2(CS)2(CO)4 structure can be derived from the experimentally characterized unbridged Cp2Cr2(CO)6 structure by replacing the two terminal carbonyl groups furthest from the Cr-Cr bond with two terminal CS groups. The two lowest energy Cp2Cr2(CS)2(CO)3 structures have a single four-electron donor η2-μ-CS group and a formal Cr-Cr single bond of length ∼3.1 Å. In contrast to the carbonyl analogue Cp2Cr2(CO)5 these Cp2Cr2(CS)2(CO)3 structures are viable with respect to disproportionation into Cp2Cr2(CS)2(CO)4 and Cp2Cr2(CS)2(CO)2 and thus are promising synthetic targets. The lowest energy Cp2Cr2(CS)2(CO)2 structures have all two-electron donor CO and CS groups and short CrCr distances around ∼2.3 Å suggesting the formal triple bonds required to give the chromium atoms the favored 18-electron configurations. These Cp2Cr2(CS)2(CO)2 structures are closely related to the known structure for Cp2Cr2(CO)4. In addition, several doubly bridged structures with four-electron donor η2-μ-CS bridges are found for Cp2Cr2(CS)2(CO)2 at higher energies. The global minimum Cp2Cr2(CS)2(CO) structure is a triply bridged triplet with a CrCr triple bond (2.299 Å by BP86). A higher energy singlet Cp2Cr2(CS)2(CO) structure has a shorter Cr-Cr distance of 2.197 Å (BP86) suggesting the formal quadruple bond required to give each chromium atom the favored 18-electron configuration. 相似文献
5.
A new polymer azido-bridged copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]
n
(I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2], in which the azido ions display three different bridging modes. 相似文献
6.
7.
Michael I. Bruce Paul A. Humphrey Allan H. White 《Journal of organometallic chemistry》2004,689(15):2558-2561
The reaction between AuMe(PPh3) and Ru3(μ-H)3(μ3-CBr)(CO)9 (1) affords the novel heptanuclear cluster Au4Ru3(μ3-CMe)(Br)(CO)9(PPh3)3 (2), containing an Au/Ru3/Au trigonal pyramidal cluster face-capped by two Au(PPh3) groups and a CMe ligand, together with Au2Ru3(μ-H)(μ3-CMe)(CO)9(PPh3)2 (3), formed by isolobal replacement of two of the three μ-H atoms in 1 by Au(PPh3) groups. The latter co-crystallises with the analogous μ3-CH complex, as also shown spectroscopically. 相似文献
8.
Oxo/hydoxo zirconium(IV) complex of the general formula [Zr6(μ3-O)4(μ3-OH)4(OOCCH2tBu)9(μ2-OH)3]2 has been isolated, when Zr(OiPr)4 reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P63/m (no. 176)). Structure consists of dimers composed of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2tBu)9] sub-units, linked by six μ2-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ2-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2tBu)9(μ2-OH)3]2 proceeds with complete conversion to ZrO2 (monoclinic form) between 603 and 803 K. 相似文献
9.
A. A. Pasynskii I. V. Skabitskii Yu. V. Torubaev I. M. Krylov G. G. Aleksandrov 《Russian Journal of Coordination Chemistry》2011,37(8):613-618
A reaction of the dimer [Mn(CO)4(SPh)]2 with (PPh3)2Pt(C2Ph2) gave the heterometallic complex (CO)4Mn(μ-SPh)Pt(PPh3)2 (I) and its isomer (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO) (II). A reaction of complex I with a diphosphine ligand (Dppm) yielded the heterometallic complex (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm) (III). Complexes I–III were characterized by X-ray diffraction. In complex I, the single Mn-Pt bond (2.6946(3) ?) is supplemented with a thiolate bridge with the shortened Pt-S and Mn-S bonds (2.3129(5)
and 2.2900(6) ?, respectively). Unlike complex I, in complex II, one phosphine group at the Pt atom is exchanged for one CO group at the Mn atom. The Mn-Pt bond (2.633(1) ?) and the thiolate
bridge (Pt-S, 2.332(2) ?; Mn-S, 2.291(2) ?) are retained. In complex III, the Mn-Pt bond (2.623(1) ?) is supplemented with thiolate (Pt-S, 2.341(2) ?; Mn-S, 2.292(2) 0?) and Dppm bridges (Pt-P,
2.240(1)?; Mn-P, 2.245(2) ?). Apparently, the Pt atom in complexes I–III is attached to the formally double bond , as in Pt complexes with olefins. 相似文献
10.
Pradeep Mathur Sathyanarayana Boodida Shaikh M. Mobin 《Journal of organometallic chemistry》2009,694(18):3043-3949
Photolysis of a hexane solution containing Fe(CO)5 and CS2 leads to desulfurization and formation of a novel cluster [{Fe2(CO)6}2(μ-C2S3)] (1). Its molecular structure was determined by single crystal X-ray diffraction methods and shown to consist of two distinct Fe2(CO)6 units linked by an unusual C2S3 unit. 相似文献
11.
Yong Leng Kelvin Tan 《Journal of organometallic chemistry》2006,691(9):2048-2054
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (4) reacts with refluxing toluene to form the clusters Ru2Os3(μ-H)2(CO)16 (5) RuOs3(CO)9(μ-CO)2(η6-C6H5Me) (6) and Ru2Os3(CO)12(μ-CO)(η6-C6H5Me) (7). Cluster 5 exists as a mixture of five isomers. The inter-relationship among the clusters has also been investigated. 相似文献
12.
M. A. Il’in E. V. Kabin V. A. Emel’yanov I. A. Baidina V. A. Vorob’yov 《Journal of Structural Chemistry》2009,50(2):328-334
Methods for the synthesis of trans-diammino complexes [RuNO(NH3)2(NO2)2(OH)] (I) and [RuNO(NH3)2(H2O)(NO3)2](NO3)·H2O (II) are suggested. The compounds were studied by IR spectroscopy and X-ray phase and X-ray structural analyses. Crystal data:
space group P-1; a = 6.2328(2) ?, b = 11.0488(3) ?, c = 11.0981(4) ?, α = 71.942(1)°, β = 83.291(1)°, γ = 86.877(1)° (I); space group P21; a = 6.6290(2) ?, b = 13.4389(5) ?, c = 7.0180(2) ?, β 114.281(1)° (II). Complex II readily lost some part of crystal water on storage in open air.
Original Russian Text Copyright ? 2009 by M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, and V. A. Vorob’yov
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 341–348, March–April, 2009. 相似文献
13.
Yong Leng Kelvin Tan 《Journal of organometallic chemistry》2007,692(4):768-773
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (1) reacts with indene under thermal activation to afford the novel clusters RuOs3(μ-H)(CO)9(μ-CO)2(η5-C9H7) (3), RuOs3(μ-H)(CO)9(μ3,η5:η2:η2-C9H7) (4) and Ru2Os3(μ-H)(CO)11(μ3,η5:η2:η2-C9H7) (5), the latter two possessing indenyl ligands in the μ3,η5:η2:η2 bonding mode. Cluster 5 exists as a mixture of two isomers. The inter-relationship among the clusters has also been investigated. 相似文献
14.
A. A. Rybinskaya E. A. Shusharina P. E. Plyusnin Yu. V. Shubin S. V. Korenev S. A. Gromilov 《Journal of Structural Chemistry》2011,52(4):816-819
A single crystal of [Pd(NH3)4]3[Ir(NO2)6]2·H2O double complex salt is studied by X-ray diffraction. Crystallographic characteristics are as follows: a = 21.0335(5) ?, b = 8.0592(2) ?, c = 21.3452(5) ?, β = 91.254(1)°, V = 3617.43(15) ?3, P21/c space group, Z = 4, d
x = 2.714 g/cm3. Single-layer pseudohexagonal packing of complex anions is determined along the [−1 0 1] direction in the structure. Complex
cations and crystallization water molecules are located between the mentioned layers. 相似文献
15.
New complexes of transition metals with organotellurium halide ligands are reported. Iodination of [CpMn(CO)2]2(μ-Ph2Te2) leads to the Te-Te bond cleavage and formation of CpMn(CO)2(PhTeI). Oxidative addition of PhTeBr3 to Fe(CO)5 gives the monomeric complex (CO)3FeBr2(PhTeBr) which is isostructural with the recently reported (CO)3FeI2(PhTeI). Insertion of phenyltellurenyl iodide (PhTeI) into the Fe-I bond of CpFe(CO)2I forms CpFe(CO)2(TeI2Ph). Molecular structures of the reported complexes were determined by single-crystal X-ray diffraction analysis (XRD). A considerable shortening of metal-tellurium distances is observed. 相似文献
16.
Yong Leng Kelvin Tan 《Journal of organometallic chemistry》2007,692(11):2253-2269
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (1) reacted readily with a number of ditertiary phosphines under chemical activation with trimethylamine-N-oxide. The solid-state and solution structures of these derivatives have been examined. Six structural types have been characterized crystallographically, including one in which a phenyl group migrates from the ditertiary phosphine ligand to the metal framework. There are many more isomers present in solution, most of which are rapidly inter-converting via hydride migrations. 相似文献
17.
Reactions of [(dtc)2Mo2(S)2(μ-S)2] with one or two equivalents of CuBr in CH2Cl2 afforded two new heterobimetallic sulfide clusters, [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] (1) and [(dtc)2Mo2(μ3-S)4(CuBr)2] (2). Both compounds were characterized by elemental analysis, IR, UV-vis and X-ray analysis. Compound 1 contains a butterfly-shaped Mo2S4Cu core in which one CuBr unit is coordinated by one bridging S and two terminal S atoms of the [(dtc)2Mo2(S)2(μ-S)2] moiety. In the structure of 2, one [(dtc)2Mo2(S)2(μ-S)2] moiety and two CuBr units are held together by six Cu-μ3-S bonds, forming a cubane-like Mo2S4Cu2 core. 相似文献
18.
A. A. Rybinskaya P. E. Plyusnin E. A. Bykova S. A. Gromilov Yu. V. Shubin S. V. Korenev 《Journal of Structural Chemistry》2012,53(3):527-533
Two new double complex salts [Pd(NH3)4]3[Rh(NO2)6]2 (I) and [Pd(NH3)4]3[Rh(NO2)6]2·H2O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?3, F-43c space group, Z = 8, d x = 2.548 g/cm3; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?3, P21/c space group, d x = 2.357 g/cm3. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd0.59Rh0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm). 相似文献
19.
The title compound was synthesized by reaction of Cu(ClO4)2, picolinic acid and carbamide in C2H5OH/CH3CN solution, and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a=14.0481(8), b=9.0130(5), c=18.626(1)?, V=2358.3(2)?3, Z=4, Dx=1.771g·cm-3, μ=1.235mm-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane, while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances, resulting in a 4+2 elongated octahedral environment. In the compound, there also exist two protonated carbamide cations for charge balance. CCDC: 195354. 相似文献
20.
E. A. Gerasimova T. V. Utkina E. V. Peresypkina A. V. Virovets T. G. Cherkasova 《Russian Journal of Inorganic Chemistry》2009,54(5):692-697
New mixed-ligand coordination compounds[Cd(DMSO)5(NCS)][Cr(NH3)2(NCS)4] · 3DMSO (I) and [Mn(DMSO)4(H2O)2][Cr(NH3)2(NCS)4]2 · 6DMSO · 2H2O (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. The crystals of compound I are monoclinic, a = 14.5275(7), b = 23.1692(11), c = 14.6969(6) ?, β = 97.057(2)°, V = 4909.4(4) ?3, space group P21/c, Z = 4, ρcalcd = 1.507 g/cm3, R = 0.0556. The crystals of compound II are triclinic, a = 11.7784(3), b = 12.1760(3), c = 13.1922(2) ?, α = 85.5420(10)°, β = 87.9000(10)°, γ = 70.3680(10)°, V = 1776.46(7) ?3, space group P
, Z = 1, ρcalcd = 1.444 g/cm3, R = 0.0350.
Original Russian Text ? E.A. Gerasimova, T.V. Utkina, E.V. Peresypkina, A.V. Virovets, T.G. Cherkasova, 2009, published in
Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 5, pp. 751–755. 相似文献