共查询到20条相似文献,搜索用时 31 毫秒
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H.J. Breunig T. Borrmann O. Moldovan R.P. Wagner 《Journal of organometallic chemistry》2009,694(3):427-91
Syntheses of [Me3SbM(CO)5] [M = Cr (1), W (2)], [Me3BiM(CO)5] [M = Cr (3), W (4)], cis-[(Me3Sb)2Mo(CO)4] (5), [tBu3BiFe(CO)4] (6), crystal structures of 1-6 and DFT studies of 1-4 are reported. 相似文献
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James D. Farwell 《Journal of organometallic chemistry》2007,692(24):5492-5494
The crystalline compounds [AlMen{Si(SiMe3)3}3−n(thf)] [n = 2 (1) or 1 (2)] were prepared from the lithium sisyl [Li{Si(SiMe3)3}(thf)3] (A) and the appropriate methylaluminium chloride [AlCl3−nMen] in thf. The X-ray structure of 1 is reported. Unlike A or a magnesium sisyl [Mg{Si(SiMe3)3}2(thf)2] (B), neither 1 nor 2 underwent an insertion reaction with an α-H-free nitrile. 相似文献
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Victor N. Khrustalev Ivan A. Portnyagin Irina V. Borisova Yuri A. Ustynyuk Valery Lunin 《Journal of organometallic chemistry》2005,690(5):1172-1177
New stable heteroleptic germanium(II) and tin(II) compounds [(SiMe3)2N-E14-OCH2CH2NMe2]n (E14 = Ge, n = 1 (1), Sn, n = 2 (2)) have been synthesized and their crystal structures have been determined by X-ray diffraction analysis. While compound 1 is monomer stabilized by intramolecular Ge ← N coordination, compound 2 is associated to dimer via intermolecular dative Sn ← O interactions. 相似文献
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Sailer Santos dos Santos Gelson Manzoni de Oliveira 《Journal of organometallic chemistry》2007,692(14):3081-3088
TeX4 (X = Cl, Br) react in HCl/HBr with [Ph(CH3)2Te]X (X = Cl, Br) to give [PhTe(CH3)2]2[TeCl6] (1) and [PhTe(CH3)2]2[TeBr6] (2). The reaction of PhTeX3 (X = Cl, Br, I) in cooled methanol with [(Ph)3Te]X (X = Cl, Br, I) leads to [Ph3Te][PhTeCl4] (3), [Ph3Te][PhTeBr4] (4) and [Ph3Te][PhTeI4] (5). In the lattices of the telluronium tellurolate salts 1 and 2, octahedral TeCl6 and TeBr6 dianions are linked by telluronium cations through Te?Cl and Te?Br secondary bonds, attaining bidimensional (1) and three-dimensional (2) assemblies. The complexes 3, 4 and 5 show two kinds of Te?halogen secondary interactions: the anion-anion interactions, which form centrosymmetric dimers, and two identical sets of three telluronium-tellurolate interactions, which accomplish the centrosymmetric fundamental moiety of the supramolecular arrays of the three compounds, with the tellurium atoms attaining distorted octahedral geometries. Also phenyl C-H?halogen secondary interactions are structure forming forces in the crystalline structures of compounds 3, 4 and 5. 相似文献
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Bimetallic alkylidene complexes of tungsten (R′O)2(ArN)WCH-SiR2-CHW(NAr)(OR′)2 (R = Me (1), Ph (2)) and (R′O)2(ArN)WCH-SiMe2SiMe2-CHW(NAr)(OR′)2 (3) (Ar = ; R′ = CMe2CF3) have been prepared by the reactions of divinyl silicon reagents R2Si(CHCH2)2 with known alkylidene compounds R′′-CHMo(NAr)(OR′)2. (R′′ = But, PhMe2C) Complexes 1-3 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1-3 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and 3 and predominant cis-units content in the case of 2. 相似文献
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Marek M. Kubicki Walter Meier Manfred Zabel 《Journal of organometallic chemistry》2007,692(18):3931-3935
The reaction of (Cp∗ = η5-C5Me5) with [Pd(DBA)2] (DBA = dibenzylidenacetone) and dppm (bis(diphenylphosphanyl)methane) gave the new tetratelluropalladate cluster (1), which has been characterised by means of elemental analysis, FD-MS and X-ray crystallography. The structure of compound 1 contains a planar PdTe4 rectangle to which two niobocene groups are coordinated. DFT calculations on the hypothetical [PdTe4]2− anion and comparison of the results with those of the W and Ni homologues show that the planar arrangement of Te ligands in 1 is due to the intrinsic property of the central Pd atom. 相似文献
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A versatile neutral metalloligand [Cu(PySal)2] (1) (PySal = 3-pyridylmethylsalicylidene-imino) was exploited as a building unit to construct five complexes {Cu[Cu(PySal)2]2}(ClO4)2 (2), {Cd[Cu(PySal)2]2(H2O)2]} (NO3)2 · 2H2O · 4CH3OH (3), {Zn[μ2-Cu(PySal)2]Cl2}n · nCH3OH (4), {Hg[μ2-Cu(PySal)2]I2}n (5) and {Cd[μ2-Cu(PySal)2]Cl2}n · nCH2Cl2 (6). [Cu(PySal)2] acts as a chelating ligand in discrete complexes 2 and 3 with unbound anions, but as a bis-monodentate bridging ligand in polymers 4, 5 and 6 when halogen anions coordinated cooperatively to metal cations. The coordination geometry of Cu2+ is well-defined square planar in bridging [Cu(PySal)2], analogous to that in free metalloligand (1), but it is distorted square planar in chelating [Cu(PySal)2]. 相似文献
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Maria S. Tarasenko Nikolay G. Naumov Dmitry Yu. Naumov Sung-Jin Kim Vladimir E. Fedorov 《Polyhedron》2008
A series of new compounds containing rare earth cations (Eu to Yb) and paramagnetic cluster anion [Re6Te8(CN)6]3− was prepared and investigated. The X-ray structural analyses have revealed that the compounds [{Ln(H2O)4}{Re6Te8(CN)6}] · 2.5H2O; Ln = Eu (1), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), [{Gd(H2O)3}{Re6Te8(CN)6}] · 2.5H2O (2) and [{Yb(H2O)4}{Re6Te8(CN)6}] (8) are three-dimensional polymers based on Re–CN–Ln interactions. Measurements of magnetic susceptibility for 2 and 5 showed that effective magnetic moment (at 300 K) was 8.13 μB for compound 2 and 10.79 μB for compound 5 with weak antiferromagnetic ordering appeared at low temperatures. 相似文献
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Michael I. Bruce Marcus L. Cole Brian W. Skelton 《Journal of organometallic chemistry》2006,691(22):4601-4614
Complexes M(CCCSiMe3)(CO)2Tp′ (Tp′ = Tp [HB(pz)3], M = Mo 2, W 4; Tp′ = Tp∗ [HB(dmpz)3], M = Mo 3) are obtained from M(CCCSiMe3)(O2CCF3)(CO)2(tmeda) (1) and K[Tp′].Reactions of 2 or 4 with AuCl(PPh3)/K2CO3 in MeOH afforded M{CCCAu(PPh3)}(CO)2Tp′ (M = Mo 5, W 6) containing C3 chains linking the Group 6 metal and gold centres.In turn, the gold complexes react with Co3(μ3-CBr)(μ-dppm)(CO)7 to give the C4-bridged {Tp(OC)2M}CCCC{Co3(μ-dppm)(CO)7} (M = Mo 7, W 8), while Mo(CBr)(CO)2Tp∗ and Co3{μ3-C(CC)2Au(PPh3)}(μ-dppm)(CO)7 give {Tp∗(OC)2Mo}C(CC)2C{Co3(μ-dppm)(CO)7} (9) via a phosphine-gold(I) halide elimination reaction. The C3 complexes Tp′(OC)2MCCCRu(dppe)Cp∗ (Tp′ = Tp, M = Mo 10, W 11; Tp′ = Tp∗, M = Mo 12) were obtained from 2-4 and RuCl(dppe)Cp∗ via KF-induced metalla-desilylation reactions. Reactions between Mo(CBr)(CO)2Tp∗ and Ru{(CC)nAu(PPh3)}(dppe)Cp∗ (n = 2, 3) afforded {Tp∗(OC)2Mo}C(CC)n{Ru(dppe)Cp∗} (n = 2 13, 3 14), containing C5 and C7 chains, respectively. Single-crystal X-ray structure determinations of 1, 2, 7, 8, 9 and 12 are reported. 相似文献
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Nicolas Merle 《Journal of organometallic chemistry》2005,690(11):2829-2834
Reaction of H2ClB · PPh2CH2PPh2 (H2ClB · dppm) with results in displacement of all three acetonitrile ligands and the formation of (1), which has been characterised crystallographically. Reaction with carbon monoxide results in a change from η2 to η1 of the borane ligand to afford (2). Compound 1 undergoes H/D exchange under a D2 atmosphere to afford , while 2 does not. 相似文献
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Ph2SiCl2 and PhMeSiCl2 react with Li2E (E = S, Se, Te) under formation of trimeric diorganosilicon chalcogenides (PhRSiE)3 (R = Ph: 1a-3a, R = Me: cis/trans-4a (E = S), cis/trans-5a (E = Se)). In case of E = S, Se dimeric four-membered ring compounds (PhRSiE)2 (R = Ph: 1b-2b, R = Me: cis/trans-4b (E = S), cis/trans-5b (E = Se)) have been observed as by-products. 1a-5b have been characterized by multinuclear NMR spectroscopy (1H, 13C, 29Si, 77Se, 125Te). Four- and six-membered ring compounds differ significantly in 29Si and 77Se chemical shifts as well as in the value of 1JSiSe.The molecular structures of 2a, 3a and trans-5a reported in this paper are the first examples of compounds with unfused six-membered rings Si3E3 (E = Se, Te). The Si3E3 rings adopt twisted boat conformations. The crystal structure of 3a reveals an intermolecular Te-Te contact of 3.858 Å which yields a dimerization in the solid state. 相似文献
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Zhi-Guo Wang Hai-Sheng Yao Qi Shen Yong Zhang 《Journal of organometallic chemistry》2006,691(15):3383-3390
The transamination of anionic homoleptic amido ytterbium complex, LiYb[N(i-Pr)2]4 with aryloxo-functionalized N-heterocyclic carbene (NHC) precursor, HO-4,6-di-tBu-C6H2-2-CH2{CH[i-Pr-NCHCHN]}Cl (H2LCl) 1 and HO-4,6-di-tBu-C6H2-2-CH2{CH[Me-NCHCHN]}Cl (H2L′Cl) 2, and BuLi in 1:2:1 molar ratio in THF at 0 °C afforded the first bisaryloxo- NHC monoamido ytterbium complexes, L2Yb [N(i-Pr)2] 3 and , respectively. The same reactions in the molar ratio of 1:1 without BuLi yields also the complex 3 and 4, not the bis-amido mono aryloxo-NHC complex {LYb[N(i-Pr)2]2} and {L′Yb[N(i-Pr)2]2}. The in situ low-temperature reaction of 2 with two equivalents of BuLi, followed by addition of one equivalent of YbCl3 in THF does not afford the expected LYbCl2, instead, [Li(DME)3][YbCl4(DME)] 5 and a dimeric imidazole-aryloxo lithium {[O-4,6-di-tBu-C6H2-2-CH2{CH(MeNCHCHNH)}]Li(THF)}26 which results from the 1,2-benzyl migration in N-heterocyclic carbene, are obtained. Complexes 3, 4, 5 and 6 have been characterized by elemental analysis and X-ray crystallography, and by NMR spectroscopy for 6. 相似文献
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Wesley T.K. Chan 《Journal of organometallic chemistry》2010,695(7):1069-1073
The reaction of the anion [(tBuP)3As]− (1) with Me2SiCl2 results in nucleophilic substitution of the Cl− anions, giving the di- and mono-substituted products [Me2Si{As(PtBu)3}2] (3a) and [Me2Si(Cl){As(PtBu)3}] (3b). Analogous reactions of the pre-isolated [(CyP)4As]− anion (2) (Cy = cyclohexyl) with Me2SiCl2 produced mixtures of products, from which no pure materials could be isolated. However, reaction of 2 [generated in situ from CyPHLi and As(NMe2)3] gives the heterocycle [(CyP)3SiMe2] (4). The X-ray structures of 3a and 4 are reported. 相似文献
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Mohammad El-khateeb Khaled Shawakfeh Heinrich Lang 《Journal of organometallic chemistry》2006,691(18):3743-3748
The hydrosulfido complexes CpRu(L)(L′)SH react with one equivalent of O-alkyl oxalyl chlorides (ROCOCOCl) to form the corresponding O-alkylthiooxalate complexes CpRu(L)(L′)SCOCO2R (L = L′ = PPh3 (1), (2); L = PPh3, L′ = CO (3); R = Me (a), Et (b)). The reactions of the hydrosulfido complexes with half equivalent of oxalyl chloride produce the bimetallic complexes [CpRu(L)(L′)SCO]2 (L = L′ = PPh3 (4), (5); L = PPh3, L′ = CO (6)). The crystal structures of CpRu(PPh3)2SCOCO2Me (1a) and CpRu(dppe)SCOCO2Et (2b) are reported. 相似文献
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Xuan Xu Liang Fang Guo-Chun Yang Zhong-Min Su 《Journal of organometallic chemistry》2006,691(9):1927-1933
To study the Ru-M interactions and their effects on 31P NMR, complexes [Ru(CO)3(Ph2Ppy)2] (py = pyridine) (1) and [Ru(CO)3(Ph2Ppy)2MCl2] (M = Zn, 2; Cd, 3; Hg, 4) were calculated by density functional theory (DFT) PBE0 method. Moreover, the PBE0-GIAO method was employed to calculate the 31P chemical shifts in complexes. The calculated 31P chemical shifts in 1-3 follow 2 > 3 > 1 which are consistent to experimental results, proving that PBE0-GIAO method adopted in this study is reasonable. This method is employed to predict the 31P chemical shift in designed complex 4. Compared with 1, the 31P chemical shifts in 2-4 vary resulting from adjacent Ru-M interactions. The Ru → M or Ru ← M charge-transfer interactions in 2-4 are revealed by second-order perturbation theory. The strength order of Ru → M interactions is the same as that of the P-Ru → M delocalization with Zn > Cd > Hg, which coincides with the order of 31P NMR chemical shifts. The interaction of Ru → M, corresponding to the delocalization from 4d orbital of Ru to s valence orbital of M2+, results in the delocalization of P-Ru → M, which decreases the electron density of P nucleus and causes the downfield 31P chemical shifts. Except 2, the back-donation effect of Ru ← M, arising from the delocalization from s valence orbital of M2+ to the valence orbital of Ru, is against the P-Ru → M delocalization and results in the upfield 31P chemical shifts in 4. Meanwhile, the binding energies indicate that complex 4 is stable and can be synthesized experimentally. However, as complex [Ru(CO)3(Ph2Ppy)2HgCl]+5 is more stable than 4, the reaction of 1 with HgCl2 only gave 5 experimentally. 相似文献
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H.W. Peindy N’Dongo 《Journal of organometallic chemistry》2009,694(6):981-1500
We describe reactions of [99mTc(H2O)3(CO)3)]+ (1) with Diels-Alder products of cyclopentadiene such as “Thiele’s acid” (HCp-COOH)2 (2) and derivatives thereof in which the corresponding [(Cp-COOH)99mTc(CO)3)] (3) complex did form in water. We propose a metal mediated Diels-Alder reaction mechanism. To show that this reaction was not limited to carboxylate groups, we synthesized conjugates of 2 (HCp-CONHR)2 (4a-c) (4a, R = benzyl amine; 4b, R = Nα-Boc-l-2,3-diaminopropionic acid and 4c, R = glycine). The corresponding 99mTc complexes [(4a)99mTc(CO)3)] 6a, [(4b)99mTc(CO)3)] 6b and [(4c)99mTc(CO)3)] 6c have been prepared along the same route as for Thiele’s acid in aqueous media demonstrating the general applicability of this synthetic strategy. The authenticity of the 99mTc complexes on the no carrier added level have been confirmed by chromatographic comparison with the structurally characterized manganese or rhenium complexes.Studies of the reaction of 1 with Thiele’s acid bound to a solid phase resin demonstrated the formation of [(Cp-COOH)99mTc(CO)3)] 3 in a heterogeneous reaction. This is the first evidence for the formation of no carrier added 99mTc radiopharmaceuticals containing cyclopentadienyl ligands via solid phase syntheses. Macroscopically, the manganese analogue 5a and the rhenium complexes 5b-c have been prepared and characterized by IR, NMR, ESI-MS and X-ray crystallography for 5a (monoclinic, P21/c, a = 9.8696(2) Å, b = 25.8533(4) Å, c = 11.8414(2) Å, β = 98.7322(17)°) in order to unambiguously assign the authenticity of the corresponding 99mTc complexes. 相似文献
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Swadhin K. Mandal Setharampattu S. Krishnamurthy Thomas Stey 《Journal of organometallic chemistry》2005,690(3):742-750
Chiral “P-N-P” ligands, (C20H12O2)PN(R)PY2 [R = CHMe2, Y = C6H5 (1), OC6H5 (2), OC6H4-4-Me (3), OC6H4-4-OMe (4) or OC6H4-4-tBu (5)] bearing the axially chiral 1,1′-binaphthyl-2,2′-dioxy moiety have been synthesised. Palladium allyl chemistry of two of these chiral ligands (1 and 2) has been investigated. The structures of isomeric η3-allyl palladium complexes, (R′ = Me or Ph; Y = C6H5 or OC6H5) have been elucidated by high field two-dimensional NMR spectroscopy. The solid state structure of [Pd(η3-1,3-Ph2-C3H3){κ2-(racemic)-(C20H12O2)PN(CHMe2)PPh2}](PF6) has been determined by X-ray crystallography. Preliminary investigations show that the diphosphazanes, 1 and 2 function as efficient auxiliary ligands for catalytic allylic alkylation but give rise to only moderate levels of enantiomeric excess. 相似文献