共查询到20条相似文献,搜索用时 31 毫秒
1.
Donna S. Amenta John W. Gilje Frank T. Edelmann Steffen Blaurock 《Journal of organometallic chemistry》2006,691(23):5065-5068
The reaction of with p-CH3C6H4S(O)2O(CH2)3C6H5 produces (η5-C5H5)(OC)3Mo(CH2)3C6H5. This is only the second structurally characterized organometallic species in which an aromatic moiety is separated by three or more methylene groups. The alkyl chain adopts a staggered conformation, the Mo-C(1)-C(2)-C(3)-C(4) unit is nearly coplanar, and the alkyl chain eclipses the trans-carbonyl group on Mo. NMR evidence indicates that this conformation is preserved in solution. 相似文献
2.
Padavattan Govindaswamy Mohan Rao Kollipara 《Journal of organometallic chemistry》2005,690(14):3465-3473
The complex [(η5-C5H5)Ru(PPh3)2Cl] (1) reacts with several arylazoimidazole (RaaiR′) ligands, viz., 2-(phenylazo)imidazole (Phai-H), 1-methyl-2-(phenylazo)imidazole (Phai-Me), 1-ethyl-2-(phenylazo)imidazole (Phai-Et), 2-(tolylazo)imidazole (Tai-H), 1-methyl-2-(tolylazo)imidazole (Tai-Me) and 1-ethyl-2-(tolylazo)imidazole (Tai-Et), gave complexes of the type [(η5-C5H5)Ru(PPh3)(RaaiR′)]+ {where R, R′ = H (2), R = H, R′ = CH3 (3), R = H, R′ = C2H5 (4), R = CH3, R′ = H (5), R, R′ = CH3 (6), R = CH3, R′ = C2H5 (7)}. The complex [(η5-C9H7)Ru(PPh3)2(CH3CN)]+ (8) undergoes reactions with a series of N,N-donor azo ligands in methanol yielding complexes of the type [(η5-C9H7) Ru(PPh3)(RaaiR′)]+ {where R, R′ = H (9), R = H, R′ = CH3 (10), R = CH3, R′ = H (11), R = CH3, R′ = C2H5 (12)}, respectively. These complexes were characterized by FT IR and FT NMR spectroscopy as well as by analytical data. The molecular structure of the complex [(η5-C5H5)Ru(PPh3)(C6H5-NN-C3H3N2)]+ (2) was established by single crystal X-ray diffraction study. 相似文献
3.
George Bashiardes Graham J. BodwellStephen P. Collingwood James F. CostelloStephen G. Davies Ai M. Fletcher Alan GarnerSimon C. Preston James E. Thomson 《Tetrahedron》2014
A range of alkyl- or aryl-substituted iron succinoyl complexes, incorporating the iron chiral auxiliary [(η5-C5H5)Fe(CO)(PPh3)], were prepared in high regio- and diastereoselectivities by employing four successful strategies: (i) the alkylation of chiral enolate equivalents with tert-butyl bromoacetate; (ii) the mutual kinetic resolution of tert-butyl α-bromoacetate with a chiral acetate enolate equivalent; (iii) the alkylation of chiral succinoyl enolate equivalents; (iv) the conjugate addition of organolithium reagents or lithium amide reagents to chiral fumaroyl derivatives. Oxidative cleavage of the iron chiral auxiliary was shown to occur without compromising the stereochemical integrity of the succinoyl fragments. 相似文献
4.
D. A. Loginov A. V. Vologzhanina P. V. Petrovskii M. M. Vinogradov A. R. Kudinov 《Russian Chemical Bulletin》2008,57(8):1653-1656
The reaction of the iodide complex [(η5-C9H2Me5)RhI2]2 (1) or the acetonitrile complex [(η5-C9H2Me5)Rh(MeCN)3]2+ with Tl[Tl(η-7,8-C2B9H11)] afforded rhodacarborane (η5-C9H2Me5)Rh(7,8-C2B9H11) (2). The cationic triple-decker complex with the bridging boratabenzene ligand [Cp*Fe(μ-η:η-C5H3Me2BMe)Rh(η5-C9H2Me5)]2+ (3) was synthesized by the reaction of the nitromethane solvate [(η5-C9H2Me5)Rh(MeNO2)3]2+ with the sandwich compound Cp*Fe(η-C5H3Me2BMe). The structure of 2 was established by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1623–1625, August, 2008. 相似文献
5.
合成了新型配合物{(n-Bu)2Sn[(η5-C5H5)Fe(η5-C5H4)COO]2}2,用元素分析、红外光谱和核磁共振谱( 1H、13C、119Sn)进行了表征,并用X-射线单晶衍射分析法测定其晶体结构。晶体属单斜晶系,空间群P21/c,晶胞参数a=11.753(4)?,b=21.133(7)?,c=23.374(9)?,β=101.62(3)°,V=5687(4)?3,Z=4,Dc=1.614Mg·m-3,μ(MoKα)=1.912mm-1,F(000)=2800,最终可靠因子R1=0.0827,wR2=0.2085。配合物分子呈中心对称,是具有Sn2O2中心内环的二聚体结构;每个锡原子与5个O原子和2个C原子形成扭曲的五角双锥几何构型,其中5个O原子为赤道配位原子,而C-Sn-C为配合物的轴。 相似文献
6.
7.
D. A. Loginov A. A. Pronin Z. A. Starikova P. V. Petrovskii A. R. Kudinov 《Russian Journal of Coordination Chemistry》2010,36(11):795-800
Cobaltacarboranes (η1, η3-cyclooctenediyl)Co(Carb) (Carb = η-9-SMe2-7,8-C2B9H10, η-1-tBuHN-1,7,9-C3B8H10) were synthesized by the reaction of the carborane anions [Carb]− with the acetonitrile complex [(η1, η3-cyclooctenediyl)Co(MeCN)3]+ generated in situ upon the dissolution of [(η1, η3-cyclooctenediyl)Co(η-1,4-C6H4Me2)]+ in MeCN. The structures of (η1,η3-cyclooctenediyl)Co(η-9-SMe2-7,8-C2B9H10 and [(η2,η2-cyclooctadiene)Co((η-1,2,4,5-C6H2Me4)]BF4 were determined by X-ray diffraction analysis. 相似文献
8.
Yu-Pin Wang Hsien-Li Leu Tso-Shen Lin Gene-Hsiang Lee 《Journal of organometallic chemistry》2008,693(15):2615-2623
With copper(I) iodide as catalyst, σ-alkynyls, compounds (η5-C5H5)Cr(NO)2(CC-C6H5) (5), [(η5-C5H4)-COOCH3]Cr(NO)2(CC-C6H5) (10), and [(η5-C5H4)-COOCH3]W(CO)3(CC-C6H5) (13), were prepared from their corresponding metal chloride 1, 6 and 12. Structures of compound 3, 5 and 12 have been solved by X-ray diffraction studies. In the case of 5, there is an internal mirror plane passing through the phenylethynyl ligand and bisecting the Cp ring. The phenyl group is oriented perpendicularly to the Cp with an eclipsed conformation. The twist angle is 0° and 118.4° for -CC-Ph and two NO ligands, respectively. The orientation is rationalized in terms of orbital overlap between ψ3 of Cp, dπ of Cr atom, and π∗ of alkynyl ligand, and complemented by molecular orbital calculation. The opposite correlation was observed on the chemical shift assignments of C(2)-C(5) on Cp ring in compounds 6 and 12, using HetCOR NMR spectroscopy. The electron density distribution in the cyclopentadienyl ring is discussed on the basis of 13C NMR data and compared with the calculations via density functional B3LYP correlation-exchange method. 相似文献
9.
I. Yu. Prikhod’ko V. P. Kirin V. A. Maksakov A. V. Virovets A. V. Golovin 《Journal of Structural Chemistry》2008,49(4):719-723
The complex Ru4(μ4-S)(μ,η3-C3H5)2(CO)12 is prepared and examined by IR and NMR spectroscopy; its crystal structure is determined (an automatic Bruker-Nonius X8 Apex
four-circle diffractometer equipped with a 2-D CCD-detector, 100 K, graphite-monochromated molybdenum source, λ = 0.71073
?). The crystal belongs to the orthorhombic crystal system with unit cell parameters a = 19.3781(9) ?, b = 12.2898(7) ?, c = 10.1726(4) ?, V = 2422.6(2) ?3, space group Pnma, Z = 4, composition C18H10O12Ru4S, d
x = 2.343 g/cm3. The molecule of point symmetry C
1 is situated on the mirror plane of the space group Pnma, two carbonyl groups at Ru2 and Ru3 atoms overlapping with the allylic ligand with a weight of 50% so that carbon atoms coincide.
Thus, we have a racemic structure with two overlapping enantiomers of the molecule of Ru4(μ4-S)(μ,η3-C3H5)2(CO)12.
Original Russian Text Copyright ? 2008 by I. Yu. Prikhod’ko, V. P. Kirin, V. A. Maksakov, A. V. Virovets, and A. V. Golovin
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 748–752, May–June, 2008. 相似文献
10.
本文利用密度泛函理论研究了异睛化合物中CN基团插入到CpW(NO)(C5H11)(η3-CH2CHCHMe)(A)中W-C键中的反应机制。研究发现,异腈插入到W-C键过程实际上是一个烷基迁移过程;相对于烯丙基,正戊基迁移到异腈碳原子上在热力学、动力学上更有利。提出了插入产物(B)与其环状异构体(C)之间的平衡转化机理,同时发现C为Fischer型金属卡宾配合物,金属中心具有d6电子构型。 相似文献
11.
12.
Paul O’Donohue Donagh Courtney Helge Müller-Bunz Michael J. McGlinchey 《Journal of organometallic chemistry》2011,696(8):1510-1527
A number of organometallic stilbenes of the general type [Co(η4-C4Ph4)(η5-C5H4CHCHR] are reported where R is C6H4X-4 (X = H, OMe, Br, NO2), 1-naphthyl, 9-anthryl, 1-pyrenyl, (η5-C5H4)Co(η4-C4Ph4), and (η5-C5H4)Fe(η5-C5H4Y) {Y = CHO, CHC(CN)2 and CHCHC5H4-η5)Co(η4-C4Ph4)}. They were prepared by Wittig or Horner-Wadsworth-Emmons reactions which yield both E and Z or only E products respectively. The isomers were separated and all compounds characterised by standard spectroscopic techniques as well as by X-ray diffraction methods in many cases. The electrochemistry of the stilbene analogues in dichloromethane solution is also reported. In most, the (η5-C5H4)Co(η4-C4Ph4) functional group undergoes a reversible one-electron oxidation. For those molecules that also include (η5-C5H4)Fe(η5-C5H4Y), this is preceded by the reversible oxidation of the ferrocenyl group. Spectroscopic and structural data suggests that for most compounds there is little electronic interaction between Co(η4-C4Ph4)(η5-C5H4) and the R end groups which are effectively independent of one another. The only exceptions to this are Z and E-[Co(η4-C4Ph4)(η5-C5H4CHCHC6H4NO2-4], and [Co(η4-C4Ph4)(η5-C5H4CHCHC5H4-η5)Fe{η5-C5H4CHC(CN)2}] where the electronic spectra are respectively consistent with a significant Co(η4-C4Ph4)(η5-C5H4)/NO2 donor/acceptor interaction and a less significant Co(η4-C4Ph4)(η5-C5H4)/C(CN)2 one. However, OTTLE studies show that in the electronic spectra of [Co(η4-C4Ph4)(η5-C5H4CHCHR]+ there are low energy absorption bands (950-1800 nm) which are attributed to R → Co(η4-C4Ph4)(η5-C5H4)+ or, when R is a ferrocenyl-base group, Co(η4-C4Ph4)(η5-C5H4) → (η5-C5H4)Fe(η5-C5H4Y)+ charge transfer transitions. The ferrocenyl compounds undergo cis/trans isomerisation on the OTTLE experiment timescale. 相似文献
13.
[(η5-C5H5)ZrCl3] reacts with [C5H4CH2CH2NMe2]Li yielding the coordination polymer [(C5H5)(C5H4CH2CH2NMe2)ZrCl2]n (1) as a brown solid which is very sensitive to moisture. The reaction of 1 with 1.35 equivalent of HCl (methanolic solution) yields pale yellow green crystals of [(η5-C5H5)(η5-C5H4CH2CH2NHMe2)ZrCl2]2[ZrCl6] (2). Compound 2 was fully characterized on the basis of NMR data and X-ray crystal structure analysis. The formation of this product indicates the elimination of C5H4CH2CH2NMe2 as well as C5H5 ligands from the Zr(IV) metal centre. 相似文献
14.
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
15.
Stephen G. Davies Jairton Dupont Robert J.C. Easton Osamu Ichihara Jeffrey M. McKenna Andrew D. Smith José A.A. de Sousa 《Journal of organometallic chemistry》2004,689(24):4184-4209
Conjugate addition of achiral lithium dimethylamide to the chiral iron cinnamoyl complexes (S,E)- and (S,Z)-[(η5-C5H5)Fe(CO)(PPh3)(COCHCHPh)] proceeds with high diastereoselectivity, with this protocol being used to establish unambiguously the absolute configuration of Winterstein’s acid (3-N,N-dimethylamino-3-phenylpropanoic acid) as (R). The highly diastereoselective conjugate addition of lithium N-benzyl-N-trimethylsilylamide to a range of α,β-unsaturated iron acyl complexes, followed by in-situ elaboration of the derived enolate by either alkylation or aldol reactions is also demonstrated, facilitating the stereoselective synthesis of both cis- and trans-β-lactams. This methodology has been used to effect the formal asymmetric syntheses of (±)-olivanic acid and (±)-thienamycin. Addition of chiral lithium amides derived from primary and secondary amines to the iron crotonyl complex [(η5-C5H5)Fe(CO)(PPh3)(COCHCHMe)] indicates that lithium N-α-methylbenzylamide shows low levels of enantiorecognition, while lithium N-3,4-dimethoxybenzyl-N-α-methylbenzylamide and lithium N-benzyl-N-α-methylbenzylamide show high levels of enantiodiscrimination. The high level of observed enantiorecognition was used to facilitate a kinetic resolution of (RS)-[(η5-C5H5)Fe(CO)(PPh3)(COCHCHMe)] with homochiral lithium (R)-N-3,4-dimethoxybenzyl-N-α-methylbenzylamide. Further mechanistic studies show that conjugate additions of (RS)-lithium N-benzyl-N-α-methylbenzylamide to either the (RS)- or homochiral iron crotonyl complex show 2:1 stoicheiometry, while homochiral lithium N-benzyl-N-α-methylbenzylamide shows 1:1 stoicheiometry. 相似文献
16.
Christoph Behrendt Jurgen Heck Michael J. McGlinchey 《Journal of organometallic chemistry》2006,691(6):1183-1196
The aldol condensation reaction between [Co(η4-C4Ph4){η5-C5H4C(O)CH3}] and a range of aromatic aldehydes [RCHO] and [RCHCH-CHO] gives a series of α,β-unsaturated ketones [Co(η4-C4Ph4){η5-C5H4C(O)CHCH-R}] and [Co(η4-C4Ph4){η5-C5H4C(O)CHCH-CHCH-R}] (3). The reaction is promoted by various bases: NaH proved to be the most effective whilst nBuLi gave [Co(η4-C4Ph4){η5-C5H4C(OH)(nBu)CH3}] as the major product. NaOH was ineffective, perhaps indicating that that the methyl protons in [Co(η4-C4Ph4){η5-C5H4C(O)CH3}] are less acidic than those in [Fe(η5-C5H5){η5-C5H4C(O)CH3}]. Compounds 3 were characterised spectroscopically. Their 1H NMR spectra are consistent with a trans configuration about their CC bond, and this was confirmed by X-ray crystallography in five cases, which showed that all have the same basic structure with parallel cyclobutadiene and cyclopentadienyl ligands, but they are not identical. The C5H4C(O)(CHCH)n-R (n = 1 or 2) moieties show little evidence for delocalisation and often deviate from planarity. The UV/Vis spectra of those 3 with smaller aromatic rings (R = C6H5, 4-C6H4NMe2, 2-C4H3S and 1-C10H7) suggest that these are donor-π-acceptor systems, but as the annellation of R increases (R = 9-C14H9, 1-C16H9 and 1-C20H11) the spectra increasingly resemble those of the parent polycyclic aromatic hydrocarbon, RH. Reduction of [Co(η4-C4Ph4){η5-C5H4C(O)CHCH-C10H7-1}] with DIBAL gives a mixture of [Co(η4-C4Ph4){η5-C5H4C(O)CH2CH2-C10H7-1}] and [Co(η4-C4Ph4){η5-C5H4CH(OH)CHCH-C10H7-1}]. A minor product from the preparation of [Co(η4-C4Ph4){η5-C5H4C(O)CH3}] was shown by X-ray crystallography to be the η4-butadiene complex [Co{η4-Ph(H)CC(Ph)-C(Ph)C(H)Ph}{η5-C5H4C(O)CH3}]. 相似文献
17.
The new ferrocenylmethylphosphines PH(CH2Fc)2 (1) [Fc = Fe(η5-C5H5)(η5-C5H4)] and P(CH2Fc)3 (2) and the phosphonium salt [P(CH2Fc)3(CH2OH)]I (3) were synthesised from P(CH2OH)3 and [FcCH2NMe3]I. [P(CH2Fc)(CH2OH)3]Cl (4) was obtained from P(CH2Fc)(CH2OH)2, CH2O and HCl. The new phosphines and phosphonium salts were fully characterised by NMR and IR spectroscopy and MS. [Mo(CO)6] reacts with 1 to give [Mo(CO)5{PH(CH2Fc)2}] (5) in high yield, but attempts to employ 2 as a ligand failed. The reaction of [P(CH2Fc)3(CH2OH)]I (3) and [PH(CH2Fc)3]I (obtained in situ from 3 and Na2S2O5) with [WI2(CO)3(NCMe)2] gave the complex salts [P(CH2Fc)3(CH2OH)][WI3(CO)4] (6) and [PH(CH2Fc)3][WI3(CO)4] (7), respectively. [P(CH2Fc)4]I (8) was synthesized from PH2CH2Fc and [FcCH2NMe3]I. Crystal structures were obtained for 1, 3-8. 相似文献
18.
Synthesis of niobocene imido cations: X-ray crystal structure of [Nb(NBu)(η-C5H4SiMe3)2(CNBu)][BPh4]
Andrés Garcés Santiago Gómez-Ruiz Antonio Antiñolo Carmen López-Mardomingo Sanjiv Prashar 《Journal of organometallic chemistry》2006,691(17):3652-3658
The reduction of [Nb(NBut)(η5-C5H4SiMe3)2Cl] by sodium amalgam followed by oxidation by [Fe(η5-C5H5)2][BPh4] in the presence of CNBut gave [Nb(NBut)(η5-C5H4SiMe3)2(CNBut)][BPh4] (1). In a similar manner, [Nb(NPh)(η5-C5H4SiMe3)2(CNBut)][BPh4] (2), [Nb(NPh)(η5-C5H4SiMe3)2(CO)][BPh4] (3) and [Nb(NBut){Me2Si(η5-C5Me4)(η5-C5H4)}(CNBut)][BPh4] (4), were prepared. The reduction of [Nb(NBut){Me2Si(η5-C5H4)2}Cl] gave, depending on the experimental conditions, either the d1-d1 dimer [(Nb{Me2Si(η5-C5H4)2}(μ-NBut))2] (5) or the hydride derivative [Nb(NBut){Me2Si(η5-C5H4)2}H] (6). The reaction of 5 with I2 led to the formation of [Nb(NBut){Me2Si(η5-C5H4)2}I] (7). The molecular structure of 1 was determined by single-crystal X-ray diffraction studies. 相似文献
19.
Fu-Chen Liu Tu-Chieh Tsai Chen-Shiang Lee Ju-Chun Wang 《Journal of organometallic chemistry》2010,695(3):423-4290
Mononuclear compounds M(CO)2(η3-C3H5)(en)(X) (X = Br, M = Mo(1), W(2); X = N3, M = Mo(3), W(4); X = CN, M = Mo(5), W(6)) and cyanide-bridged bimetallic compounds [(en)(η3-C3H5)(CO)2M(μ-CN)M(CO)2(η3-C3H5)(en)]Br (M = Mo (7), W(8)) were prepared and characterized. These compounds are fluxional and display broad unresolved proton NMR signals at room temperature. Compounds 1-6 were characterized by NMR spectroscopy at −60 °C, which revealed isomers in solution. The major isomers of 1-4 adopt an asymmetric endo-conformation, while those of 5 and 6 were both found to possess a symmetric endo-conformation. The single crystal X-ray structures of 1-6 are consistent with the structures of the major isomer in solution at low temperature. In contrast to mononuclear terminal cyanide compounds 5 and 6, cyanide-bridged compounds 7 and 8 were found to adopt the asymmetric endo-conformation in the solid state. 相似文献
20.
Esther Delgado Elisa Hernández María Villa Beatriz Alonso 《Journal of organometallic chemistry》2007,692(24):5453-5458
Processes such as S-C and C-H bond activations as well as C-C coupling reactions have taken place in the synthesis of the new compound [Os3(CO)9(μ3-η2,η3,η3-{C5H5FeC5H3CCC(S)C(Fc)CHO}] (Fc = C5H4FeC5H5), which contains an aldehyde oxametallacycle. A reactivity study of it has been carried out. In addition, other new triosmium clusters such as [Os3(CO)9(μ3,η2-CCFc)(μ,η1-SCCFc)], [Os3(CO)10(μ,η2-CCFc)(μ,η1-SCCFc)] and [Os3(CO)9(μ-CO)(μ3,η2-FcCCSCCFc)] have been prepared from the reaction of [Os3(CO)10(NCMe)2] and FcCCSCCFc. All the compounds have been characterized by analytical and spectroscopic techniques. The crystal structures of [Os3(CO)9(μ3,η2-CCFc)(μ,η1-SCCFc)] and [Os3(CO)9(μ3-η2,η3,η3-{C5H5FeC5H3CCC(S)C(Fc)CHO}] have been determined by X-ray crystallography and some electrochemical studies have also carried out. 相似文献