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1.
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
2.
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
3.
Padmamalini Srinivasan 《Journal of organometallic chemistry》2006,691(5):941-951
The mixed metal cluster Cp*IrOs3(μ-H)2(CO)10 (1) reacted readily with a number of group 16 substrates under chemical activation with TMNO. It reacted with C6H5SH to afford the novel cluster Cp*IrOs3(μ-H)3(CO)9(μ-SPh) (2). It also reacted readily with Ph3PSe to afford five new clusters, viz., Cp*IrOs3(μ-H)2(CO)9(μ3-Se) (3) Os3(μ-H)2(CO)7(μ3-Se)(PPh3)2 (4), Cp*IrOs3(μ-H)2(CO)9(PPh3) (5), Cp*IrOs3(μ-H)2(μ3-Se)(CO)8(PPh3) (6) and Cp*IrOs3(μ-H)2(μ3-Se)2(CO)7(PPh3) (7). The reaction pathway for this reaction has been studied carefully and suggests that Ph3PSe functioned primarily as a selenium atom transfer agent to give initially the even more reactive 3. The reaction of 1 with di-p-tolyl ditelluride yielded three new clusters, 8-10, which were non-interconverting stereoisomers with the formulation Cp*IrOs3(μ-H)2(μ-Te-p-C6H4CH3)2(CO)8. 相似文献
4.
Gloria Sánchez-Cabrera Francisco J. Zuno-Cruz María J. Rosales-Hoz 《Journal of organometallic chemistry》2007,692(11):2138-2147
The compound [Os3(CO)10(μ-Cl)(μ-AuPPh3)] (2) was prepared from the reaction between [Os3(CO)10(NCMe)2] (1) and [AuClPPh3] under mild conditions. The reaction of 2 with 4-mercaptopyridine (4-pyS) ligand yielded compounds [Os3(CO)10(μ-H)(μ-SC5H4N)] (4), formed by isolobal replacement of the fragment [AuPPh3]+ by H+ and [Os3(CO)10(μ-AuPPh3)(μ-SC5H4N)] (5). [Os3(CO)10(μ-H)(μ-SC5H4N)] (4) was also obtained by substitution of two acetonitrile ligands in the activated cluster 1 by 4-pyS, at room temperature in dichloromethane. Compounds 2-5 were characterized spectroscopically and the molecular structures of 4 and 5 in the solid state were obtained by single crystal X-ray diffraction studies. 相似文献
5.
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
6.
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
7.
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
8.
9.
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10.
Michael I Bruce Andrew C Meier Allan H White 《Journal of organometallic chemistry》2004,689(5):965-970
The reaction between Ru3(μ-H){μ3-C2CPh2(OH)}(CO)9 and HCCPh, carried out in the presence of HBF4 · Me2O, afforded the cluster complexes Ru3(μ-H)(μ3-CPh2CCCCPh)(CO)9 (5) and Ru3{μ3-CPhCHCC(CPh2)CHCPh}(μ-CO)(CO)8 (6), both of which were characterised by single-crystal X-ray studies. 相似文献
11.
Yury Torubaev Pradeep Mathur Alexander Pasynskii. 《Journal of organometallic chemistry》2011,696(4):832-834
Treatment of ruthenium carbonyl, [Ru3(CO)12] with phenylseleno tribromide PhSeBr3 afforded a new triruthenium cluster, [(CO)10Br4Ru3(μ-SePh)2] (1). Its molecular structure was determined by single crystal XRD method (P21/c; a = 10.514(3) Å; b = 10.814(3) Å; c = 19.063(5) Å; β = 105.064(4)°; V = 2093.1(10) Å3) and shown to have two lateral Ru(CO)3Br2 units attached via two PhSe bridges to a Ru(CO)4 center forming a chain-like Ru-Se-Ru-Se-Ru cluster core. This is in contrast with a recently reported reaction of PhTeBr3 with [Ru3(CO)12] which formed a monomeric complex of ruthenium-dicarbonyl-dibromo fragment coordinating two PhTeBr ligands, [(CO)2RuBr2(PhTeBr)2]. 相似文献
12.
Li-Cheng Song Hua-Wei Cheng Qing-Mei Hu Zhi Wang 《Journal of organometallic chemistry》2004,689(1):139-145
The monoanions (η5-RC5H4)(CO)3Cr− (1, R=H; 2, R=Me; 3, R=CO2Et) reacted with tetrahedral cluster FeCo2(μ3-S)(CO)9 to give single isolobal displacement products (η5-RC5H4)FeCrCo(μ3-S)(CO)8 (4, R=H; 5, R=Me; 6, R=CO2Et) in 86-89% yields, whereas monoanion (η5-RC5H4)(CO)3Cr− (7, R=C(O)Me) reacted with FeCo2(μ3-S)(CO)9 to afford the expected single isolobal displacement product (η5-RC5H4)FeCrCo(μ3-S)(CO)8 (8, R=C(O)Me) in 5% yield and an unexpected square pyramidal cluster FeCo2(μ3-S)2(CO)9 (9) in 45% yield. Similarly, the dianions [η5-C5H4CH2(CH2OCH2)nCH2C5H4-η5][(CO)3Cr−]2 (10, n=1; 11, n=2; 12, n=3) reacted with two molecules of FeCo2(μ3-S)(CO)9 to produce double isolobal displacement products [η5-C5H4CH2(CH2OCH2)nCH2C5H4-η5][FeCrCo(μ3-S)(CO)8]2 (13, n=1; 14, n=2; 15, n=3) in 32-36% yields, while treatment of dianion [η5-C5H4C(O)CH2]2[(CO)3Cr−]2 (16) with two molecules of FeCo2(μ3-S)(CO)9 gave the unexpected square pyramidal cluster FeCo2(μ3-S)2(CO)9 (9) in 42% yield and the corresponding double isolobal displacement product [η5-C5H4C(O)CH2]2[FeCrCo(μ3-S)(CO)8]2 (17) in 8% yield. Products 4-6, 8, 9, 13-15 and 17 were characterized by elemental analyses, IR and 1H NMR spectroscopy, as well as for 4, 6 and 9 by X-ray diffraction techniques. 相似文献
13.
14.
Xu Feng Chen Yong-Mei Yang Shi-Yan Sun Wen-Hua Yu Kai-Bei 《Transition Metal Chemistry》2000,25(1):108-111
CpMoFeCo(CO)7(3-S) reacts with Cp*M(CO)3Cl or CpM(CO)3Cl (M=W, Mo) to gave the mixed-metal clusters Cp*WCpMoFe(CO)7(3-S) (1), Cp*MoCpMoFe(CO)7(3-S) (2), CpWCp*MoFe(CO)7(3-S) (3), CpMoCp*MoFe(CO)7(3-S) (4) and Cp*WCp*MoFe(CO)7(3-S) (5). The title clusters have been characterized by i.r., 1H/13C-n.m.r. spectroscopy and their compositions have been confirmed by elemental analyses. The X-ray crystal structure analysis shows the two independent enantiomeric molecules of clusters (1) in one crystal structure unit. 相似文献
15.
Charles E. Ellul 《Journal of organometallic chemistry》2010,695(1):6-2376
The reduction of trans-[Pd(NHC)2Cl2] (NHC = IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IiPr2 = 1,3-bis-isopropylimidazol-2-ylidene) with potassium graphite under an atmosphere of CO affords the palladium NHC carbonyl clusters [Pd3(μ-CO)3(NHC)3] (NHC = IMes, 1; IiPr2, 3). Treatment of 1 with SO2 at room temperature yields the bridging SO2 complex [Pd3(μ-SO2)3(IMes)3] (4) in quantitative yield. Complexes 1, 3 and 4 have been structurally characterised by X-ray crystallography. 相似文献
16.
T. Yu. Glazunova A. I. Boltalin S. I. Troyanov 《Russian Journal of Coordination Chemistry》2005,31(4):247-252
Novel anhydrous trinuclear 3-oxo complexes of Cr(III), Cr3(3-O)(CF3COO)6(CH3COOH)2(CF3COO) (I) and of Cr(III,III,II), Cr3(3-O)(CF3COO)6(CH3COOH)2(THF) (II) (where THF is (CH2)4O) are synthesized by anodic dissolution of metallic chromium in solutions of trifluoroacetic acid in acetonitrile and in tetrahydrofuran and their structures are studied by X-ray diffraction analysis. Complex I forms orthorhombic crystals with space group Pna21, a = 9.778(1) , b = 16.042(2) , c = 22.851(4) , Z = 4, R
1 = 0.0332; complex II crystallizes in monoclinic system: space group P21/c, a = 9.866(1) , b = 17.895(2) , c = 21.167(4) , = 100.75(2)°, Z = 4, R = 0.0422. The average Cr-(3-O) distances in compounds I and II are almost equal (1.943(3) and 1.927(3) ). An average length of the Cr-O bond in octahedral surrounding of metal atoms is different in complexes I and II (1.985(4) and 2.003(3) , respectively), which is specified by different oxidation states of the metal atom. The CrCr distances lie in an interval of 3.366(1)–3.337(1) .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 266–272.Original Russian Text Copyright © 2005 by Glazunova, Boltalin, Troyanov. 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.
Francesco Avanzini Maurizio Casarin Daniel Forrer Luciano Pandolfo Mauro Sambi Andrea Vittadini 《Theoretical chemistry accounts》2012,131(3):1166
Experimental and theoretical results pertaining to [Zn10(μ4-S)(μ3-S)6(Py)9(SO4)3], a possible molecular model of ZnS S-terminated polar surfaces, as well as a potential source of strictly monodispersed
ZnS quantum dots, are presented and discussed. The results of density functional theory (DFT) calculations provided a rationale
for the peculiar arrangement of [Zn10(μ4-S)(μ3-S)6(Py)9(SO4)3] clusters in the solid state, contemporarily indicating the unsuitability of the isolated species to mimic whatever (polar
or non-polar) ZnS surface. Despite the fact that such a failure is further confirmed by time-dependent DFT and UV–Vis diffuse
reflectance spectroscopy, the combined use of theoretical outcomes, DRIFT measurements, and literature data pertaining to
the surface chemical properties of ZnS (Hertl in Langmuir 4:594, 1988) ultimately testifies that [Zn10(μ4-S)(μ3-S)6(Py)9(SO4)3] is perfectly suited to model the interaction of pyridine molecules with ZnS surface Lewis acid sites. The herein reported
theoretical results are expected to be a useful reference for the interpretation of chemisorption experiments of Py-based
Lewis bases on single crystal ZnS surfaces. 相似文献
19.
20.
P. A. Abramov M. N. Sokolov A. V. Virovets V. P. Fedin 《Journal of Structural Chemistry》2009,50(1):162-165
The crystal structure of [(C5Me4Et)3Rh3(μ3-Se)2](PF6)2 and [(C5Me4Et)2Rh2(μ2-Cl)3]PF6, obtained in the reaction of [(C5Me4Et)Rh(C6H6)](PF6)2 with ZnSe in 4M HCl under hydrothermal conditions, is determined. In agreement with the 18VE rule, the triangular cluster
contains single metal-metal bonds (Rh-Rh 2.864(1) ?), whereas they are absent in the binuclear complex (Rh ...Rh 3,216(1)
?).
Original Russian Text Copyright ? 2009 by P. A. Abramov, M. N. Sokolov, A. V. Virovets, and V. P. Fedin
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 1, pp. 169–172, January–February, 2009. 相似文献