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1.
The reaction of Ru(5)(CO)(15)(mu(5)-C), 1, with Ph(3)GeH at 150 degrees C has yielded two new germanium-rich pentaruthenium cluster complexes: Ru(5)(CO)(11)(mu-CO)(mu-GePh(2))(3)(mu(5)-C), 2; Ru(5)(CO)(11)(mu;-GePh(2))(4)(mu(5)-C), 3. Both compounds contain square pyramidal Ru(5) clusters with GePh(2) groups bridging three and four of the edges of the Ru(5) square base, respectively. When treated with 1 equiv of Ph(3)GeH at 150 degrees C compound 2 is converted to 3. Reaction of 3 with H(2) at 150 degrees C yielded Ru(5)(CO)(10)(mu-GePh(2))(4)(mu(5)-C)(mu-H)(2), 4, containing two hydride ligands and one less CO ligand. Reaction of 4 with hydrogen at 150 degrees C yielded the compound Ru(5)(CO)(10)(mu-GePh(2))(2)(mu(3)-GePh)(2)(mu(3)-H)(mu(4)-CH), 5, by loss of benzene and conversion of two of the bridging GePh(2) groups into triply bridging GePh groups. Compound 5 contains one triply bridging hydride ligand and a quadruply bridging methylidyne ligand formed by addition of one hydrogen atom to the carbido carbon atom. 相似文献
2.
The sulfur of acetophenone thiosemicarbazone {(Ph)(Me)C=N-NH-C(=S)NH(2); Haptsc} and two iodine atoms form an unusual heterobridge in the dinuclear complex [(Ph(3)P)Cu(mu-I)(2)(mu-S-Haptsc)Cu(PPh(3))] (1), leading to a short Cu--Cu distance of 2.504(1) Angstrom. This uncommon heterobridging is attributed to the presence of a methyl substituent at the Schiff base C2 carbon atom of the acetophenone thiosemicarbazone. 相似文献
3.
The compounds Co(TpivPP) (1), Co(TpivPP)(NO2)(1-MeIm) (2), and Co(TpivPP)(NO2)(1,2-Me2Im) (3) have been synthesized (TpivPP = meso-tetrakis(alpha, alpha, alpha, alpha-o-pivalamidophenyl)porphyrinato dianion), and their structures have been determined with single-crystal X-ray diffraction methods. 1: a = 17.578(1) A, b = 17.596(1) A, c = 20.639(1) A, beta = 115.03(1) degrees, P2(1)/c, Z = 4, T = -120 degrees C. 2: a = 18.522(4) A, b = 18.942(4) A, c = 18.177(4) A, beta = 90.68(3) degrees, C2/c, Z = 4, T = -70 degrees C. 3: a = 18.998(4) A, b = 19.187(4) A, c = 18.000(4) A, beta = 90.96(3) degrees, C2/c, Z = 4, T = -120 degrees C. Compounds 2 and 3 have crystallographically imposed 2-fold axes. In 2 and 3, which represent R-state (relaxed) and T-state (tense) models, respectively, for hemoglobin, the NO2 ligand is bound on the "picket" side to the Co atom, and either 1-MeIm (for 2) or 1,2-Me2Im (for 3) is bound to the Co atom at the sixth coordination site on the sterically unhindered side of the molecule. The average deviations of atoms from the 24-atom porphyrin core are 0.031, 0.129, and 0.117 A for 1, 2, and 3, respectively. The Co atom is -0.043(1) A out of the mean 24-atom porphyrin plane toward the 1-MeIm ligand in 2 and -0.089(1) A out of the plane toward the 1,2-Me2Im ligand in 3. The bonds of both axial ligands in the R-state model 2, 1.898(4) A for Co-N(O2) and 1.995(4) A for Co-N(base), are shorter than the corresponding bonds in the T-state model 3, 1.917(4) A for Co-N(O2) and 2.091(4) A for Co-N(base). 相似文献
4.
13C NMR differences of chemical shifts (delta(X) - delta(H)) of allyl carbon atoms in a series of trans-(1-(diphenylphosphino)-2-(dimethylamino)ethane)(eta(3)-1-arylallyl)palladium tetrafluoroborates, X ranging from NO(2) to OMe, correlate very well with sigma Hammett constants for C-1 and with sigma(+) for C-3, this carbon atom being in a trans relationship with the positively charged nitrogen atom. 相似文献
5.
Reactions of W(CO)(6) with formamidines contrast with those of Mo(CO)(6) and Cr(CO)(6) in that the former do not yield quadruply bonded dimetal species. From the reaction of W(CO)(6) with HDAniF (HDAniF = N,N'-di-p-anisylformamidine), several new ditungsten carbonyl compounds (W(2)(mu-CO)(2)(mu-DAniF)(2)(eta(2)-DAniF)(2) (1), W(2)(mu-CO)(2)(mu-DAniF)(2)(eta(2)-DAniF)(eta(2)-CH(2)DAniF) (2), and W(2)(mu-CO)(mu-CNC(6)H(4)OCH(3))(mu-DAniF)(2)(eta(2)-DAniF)(2) (3)) have been isolated and fully characterized. In 2, CH(2)DAniF represents a DAniF ligand in which a methylene group has been added to one of the nitrogen atoms. This ligand binds to the tungsten atom using a nitrogen and a carbon atom. Compound 1 has a tungsten-tungsten bond distance of 2.476(1) A and a planar W(2)(mu-CO)(2) core structure which has C(2)(h)() symmetry with short and long W-C bond distances (1.99(1) and 2.28(1) A, respectively). DFT calculations on a model of 1 indicate that (a) the C(2)(h)() instead of D(2)(h)() symmetry of the ditungsten core may be attributed to W --> CO pi back-bonding interactions and (b) the bond between the tungsten atoms may be formulated as a double bond. The new tetragonal paddlewheel compound W(2)(DAniF)(4) (4) and the edge-sharing bioctahedron W(2)(mu-O)(mu-NC(6)H(3)Cl(2))(mu-D(Cl)PhF)(2)(eta(2)-D(Cl)PhF)(2) (5) (D(Cl)PhF = N,N'-di-(3,5-dichlorophenyl)formamidinate) have also been prepared. 相似文献
6.
Wen‐Zhen Wang Xin Liu Dai‐Zheng Liao Zong‐Hui Jiang Shi‐Ping Yan Geng‐Lin Wang 《无机化学与普通化学杂志》2003,629(9):1585-1588
A new ruthenium(II) complex [Ru(NO2)4(CO)(H2O)]Cl2 · 2H2O has been prepared and characterized structurally. The compound crystallizes in monoclinic space group C2 /m, with the unit cell parameters a = 12.913(2), b = 14.605(2), c = 7.4494(1)Å, ß =121.49(2)°; V = 1198.0(3)Å3, Z = 4, Dc = 2.429 Mgm—3; μ = 1.83 mm—1; R = 0.0455, wR = 0.1552. The complex contains four neutral NO2 ligands. The ruthenium atom is six‐coordinated to four nitrogen atoms of nitrogen dioxide, one carbon atom from carbon monoxide and one oxygen atom from water molecule, forming slightly distorted octahedral coordination. The preparation procedure has been discussed. 相似文献
7.
Q. Chang J. Chen M. Xie W. Liu Y. Yu Q. Ye X. Chen 《Journal of Structural Chemistry》2011,52(4):824-827
Ir(acac-O,O)2(acac-C3)(pyridine), 1 is synthesized, and its crystal structure is determined by single crystal X-ray diffraction. In the complex, the central
Ir(III) atom displays a distorted octahedral geometry wherein the equatorial positions are occupied by four oxygen atoms of
two acetylacetone ligands, and the apical positions are coordinated by a carbon atom of one acetylacetone ligand and a nitrogen
atom of pyridine. 相似文献
8.
Jack L. Davidson William F. Wilson Ljubica Manojlović-Muir Kenneth W. Muir 《Journal of organometallic chemistry》1983,254(1):C6-C10
η2 -Vinyl complexes [MCl{η2 -C(CF3)C(CF3)L} (CF3CCCF3)(η5 -C5H5)] (M = Mo, W: L = tertiary phosphine or phosphite or pyridine) have been shown by NMR and X-ray diffraction studies to exist in two distinct isomeric forms which exhibit (a) different orientations of the η2 -vinyl ligand (b) different configurations at the asymmetric carbon atom of the η2 -vinyl ligand: variable temperature NMR studies reveal fluxional behaviour thought to involve reversible inversion of configuration at this carbon atom. 相似文献
9.
1 INTRODUCTION A number of isonitroso-b-diketones and isonitroso-b-ketoesters such as isonitrosoacetyl- acetone(Hiaa), isonitrosobenzoylacetone(Hiba) and isonitrosoethylacetoacetate (Hieaa) have been employed as reagents in spectrophotometric determination of iron, palladium and ruthenium[1]. Transition metal complexes of such ligands[2] are potential models for metal binding sites in ferroverdin[3]. They were found as dyes and light-absorbing agents for the acceleration of the sol… 相似文献
10.
MA Dong |sheng Gao Shan + {** } HUO Li |hua GAO Jing |sheng College of Chemistry Chemical Engineering Heilongjiang University Harbin P. R. China 《高等学校化学研究》2004,20(3):341-344
IntroductionAsthevanadate dependentenzyme ,ahaloperox idase,andvanadiumnitrogenasehavebeenfoundinsuccession ,somescientistsareinterestedinthecoor dinationchemistryandthebiochemistryofvanadi um[1] .Thereactivecenterofvanadiumbromoperoxi dasecontainstheoxovanadiumVO3+ coordinatedbyoxygenandnitrogenatoms[2 ] .However,thestudiesaboutoxovanadiumVO3+ coordinationcompoundscontainingbioactiveligandsarerarelyfound[3— 8] .Hydroximicacidthatcanbeconsideredtobethederivativeofthecarboxylicacid ,theamide… 相似文献
11.
Capps KB Whitener GD Bauer A Abboud KA Wasser IM Vollhardt KP Hoff CD 《Inorganic chemistry》2002,41(12):3212-3217
Reaction of FvW(2)(H)(2)(CO)(6) with 2/8S(8) in THF results in rapid and quantitative formation of FvW(2)(SH)(2)(CO)(6). The crystal structure of this complex is reported and shows that the two tungsten-hydrosulfide groups are on opposite faces of the fulvalene ligand in an anti configuration. Nevertheless, treatment of FvW(2)(SH)(2)(CO)(6) (1) with PhN[double bond]NPh produces FvW(2)(mu-S(2))(CO)(6) (2) and Ph(H)NN(H)Ph. The crystal structure of the bridging disulfide, which cocrystallizes with 1 in a 2:1 ratio, is also described. Exposure of 2 equiv of *CrCp*(CO)(3) to 1 effects similar H atom transfers yielding 2 HCrCp*(CO)(3) and 2. Attempts to obtain crystals of the latter from solutions derived from this reaction mixture furnished a third product, FvW(2)(mu-S)(CO)(6) (3), which was analyzed crystallographically. The enthalpy of sulfur atom insertion into FvW(2)(H)(2)(CO)(6), yielding 1, has been measured by solution calorimetry. 相似文献
12.
Dainis Dakternieks Andrew Duthie Douglas R. Smyth Clynton P. D. Stapleton Edward R. T. Tiekink 《应用有机金属化学》2004,18(1):53-54
The tin atom in the title compound is in a distorted pentagonal bipyramidal geometry defined by two sets of nitrogen and oxygen donors derived from the carboxylate ligands, two carbon atoms from the cyclohexyl substituents and an oxygen atom from the coordinated water molecule; C? Sn? C 170.85(15)°. Extensive hydrogen bonding occurs in the lattice. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
13.
1 INTRODUCTION There has been considerable interest of copper(II) -hydroxylate complexes in the structural chemistry and biochemistry. There are two structural types in copper(II) -hydroxylate com- plexes: mononuclear[1~6] and dinuclear structure[7~9]. The present work is a part of our study on the copper complexes of -hydroxylated acid and reports the synthesis and structure of a mononuclear copper(II) complex with 9-hydroxy- fluorene-9-carboxylato acid, [Cu(C14H8O3)(C5H13- NO)(H… 相似文献
14.
用一维NMR方法研究了新型电化学发光探针Ru(dcbpy)(phen)2(PF6)2的立体结构,借助二维^1H-^1H COSY和^1H-^13C COSY实验对其氢谱和碳谱进行了完全的归属,并给出了其氢谱和碳谱的化学位移值。 相似文献
15.
16.
The crystal structure of [Ni(C5H2N2O4)(2, 2?-bipy)(H2O)2]·2H2O 1 has been determined by X-ray diffraction. Crystal data: triclinic system, space group P ī with a = 7.9424(3), b = 9.9417(3), c = 12.1867(3) (A。), α = 84.771(1), β = 77.375(2), γ = 68.993(2)°, C15H18N4O8Ni, Mr = 440.7, V = 876.16(5) (A。)3, Z = 2, Dc = 1.672 g/cm3, F(000) = 456, ((MoK() = 1.162 mm-1, the final R = 0.0464 and wR = 0.1055 for 3026 observed reflections with I > 2((I). In the title compound, the nickel ion is coordinated by a nitrogen atom and an oxygen atom from the orotate ligand, two nitrogen atoms from 2, 2'-bipy and two oxygen atoms from the coordinated water molecules in a distorted octahedral geometry. The presence of intermolecular hydrogen bonding and (-( stacking interaction of aromatic rings from 2, 2'-bipy results in a 3D structure. 相似文献
17.
M. R. Galding A. V. Virovets I. V. Kazakov M. Scheer S. N. Smirnov A. Y. Timoshkin 《Acta Crystallographica. Section C, Structural Chemistry》2016,72(7):514-517
Vaska‐type complexes, i.e. trans‐[RhX(CO)(PPh3)2] (X is a halogen or pseudohalogen), undergo a range of reactions and exhibit considerable catalytic activity. The electron density on the RhI atom in these complexes plays an important role in their reactivity. Many cyanotrihydridoborate (BH3CN−) complexes of Group 6–8 transition metals have been synthesized and structurally characterized, an exception being the rhodium(I) complex. Carbonyl(cyanotrihydridoborato‐κN)bis(triphenylphosphine‐κP)rhodium(I), [Rh(NCBH3)(CO)(C18H15P)2], was prepared by the metathesis reaction of sodium cyanotrihydridoborate with trans‐[RhCl(CO)(PPh3)2], and was characterized by single‐crystal X‐ray diffraction analysis and IR, 1H, 13C and 11B NMR spectroscopy. The X‐ray diffraction data indicate that the cyanotrihydridoborate ligand coordinates to the RhI atom through the N atom in a trans position with respect to the carbonyl ligand; this was also confirmed by the IR and NMR data. The carbonyl stretching frequency ν(CO) and the carbonyl carbon 1JC–Rh and 1JC–P coupling constants of the Cipso atoms of the triphenylphosphine groups reflect the diminished electron density on the central RhI atom compared to the parent trans‐[RhCl(CO)(PPh3)2] complex. 相似文献
18.
V.G. Andrianov Yu.T. Struchkov N.E. Kolobova A.B. Antonova N.S. Obezyuk 《Journal of organometallic chemistry》1976,122(2):C33-C36
The binuclear complex with composition [Cp(CO)2 MnC(CO)CHPh]Fe(CO)3 is obtained by interaction of CpMn(CCHPh)(CO)2 with Fe2C0)9. An X-ray study of this complex has shown that besides three carbonyl groups the iron atom is covalently bonded to four atoms, viz. the carbon of a phenylmethylene group, the carbon of a bridging CO group, the manganese atom and the central carbon of the organomanganese ligand lying just above iron. It seems to be the first example of a heteroatomic analogue of trimethylenemethane complexes. 相似文献
19.
Il’in E. G. Parshakov A. S. Privalov V. I. Goryunov E. I. Goryunova I. B. Nifant’ev E. E. 《Russian Journal of Coordination Chemistry》2019,45(9):667-674
Russian Journal of Coordination Chemistry - The complex formation of TiF4 with the phosphorylated ketone Ph2P(O)CH(Me)CH2C(O)Et (L), containing an asymmetric carbon atom in the aliphatic... 相似文献
20.
1 INTRODUCTION Orotic acid (H3dtpc), an important pyrimidine derivative as the effective precursor in the biosynthesis of pyrimidine base of nucleic acids in living organisms, plays a unique role in bioinorganic and pharmaceutical. Aside from the biological interest, orotic acid is also interesting in coordination chemistry. Its ketonic and enolic tautomers along with asymmetric geometry make it to be a very good versatile polydentate ligand[1~5]. The incorporation of metals into supram… 相似文献