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1.
《Journal of organometallic chemistry》1990,393(1):C6-C9
The zirconium silyl complex CpCpZr[Si(SiMe3)3]Me (1; Cp = η5-C5H5; Cp = η5-C5Me5) reacts with nitriles RCN (R = Me, CHCH2, Ph) to form the azomethine derivatives CpCpZr[NC(R)Si(SiMe3)3]Me (2, R = Me; 3, R = CHCH2; 4, R = Ph). Pyridine reacts with 1 to give a 75% yield of CpCpZr[NC5H5Si(SiMe3)3]Me (5), which results from 1,2-addition of the ZrSi bond of 1 to pyridine. These reactions provide the first examples of nitrile and pyridine insertions into a transition metal-silicon bond. The related silyl complexes Cp2Zr[Si(SiMe3)3]Me and CpCpZr[Si(SiMe3)3]Cl are much less reactive toward nitriles and pyridine. 相似文献
2.
Rainer Bartsch Christian Müller Axel Fischer Peter G. Jones 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently1. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η5-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η5-C5Me5) (η5-C2 tBu2P3]. In the ruthenium complex [Fe(η5-C5Me5)(η5-C2 tBu2P3) Ru3(CO)9] 2 two adjacent phosphorus atoms of the η5-C2 tBu2P3 ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(CO)2]2 3 represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres. 相似文献
3.
4.
《Polyhedron》1987,6(8):1703-1705
The acetone complex [Fe(CO)2(Me2CO)(η5-C5H5)][PF6] reacts with L (L = H2NNHCSNH2, cy-C5H10CNNHCSNH2, or R′R″CNNHCSNH2 where R′ = R″ = Me; R′ = H, R″ = Ph; R′ = H, R″ = p-NO2Ph; R′ = p-MePh) in refluxing trichloromethane to give the new complexes [Fe(CO)2L(η5-C5H5)][PF6]. The complexes are clearly coordinated through the sulphur atom since the thiosemicarbazide complex reacts with benzaldehyde to afford the corresponding thiosemicarbazone compound. 相似文献
5.
《Journal of organometallic chemistry》1986,316(3):315-318
The complex t-Bu(η5-C5H5)FE(CO)2 has been treated with triphenylphosphine in refluxing THF to produce t-BuCO(η5-C5H5)Fe(CO)(PPh3). The large steric bulk of the t-butyl group suggests that this reaction should be faster than the reaction involving the methyl group, and a kinetic investigation illustrates this to be the case. The same steric bulk predicts that the reaction with SO2 should be slow, and indeed we have been unable to effect the related SO2 insertion reaction. Attempts to prepare the corresponding t-Bu(η5-C5H5)W(CO)3 led to formation of the related isobutyl complex. 相似文献
6.
《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1989,45(2):249-252
The absolute integrated i.r. intensities of the CO and CS stretching bands of the thiocarbonyl complexes (η6C6H5R)Cr(CO)2(CS), where R = H, Me, Cl and CO2Me, have been determined in CS2 solutions. The intensities have been correlated with each other and with the band wavenumbers, and have been shown to be dependent on the nature of the substituent R in the aromatic ring. The intensities have been demonstrated to be better probes of the electronic effects occurring in these complexes than are the wavenumbers, and correlate well with the Hammett substituent parameters, σ0. 相似文献
7.
T. Yu. Orlova Yu. S. Nekrasov P. V. Petrovskii M. G. Ezernitskaya Z. A. Starikova O. L. Lependina 《Russian Chemical Bulletin》2008,57(1):63-67
The metallation of the η5-C5H5(CO)2Fe-η1,η5-C5H4Mn(CO)3 complex with BunLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph2PCl afforded the η5-Ph2PC5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 complex. The reaction of the latter with η5-C5H5(CO)3WCl in the presence of Me3NO produced the trinuclear complex η5-C5H5Cl(CO)2W-η1,η5-(Ph2P)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3. The structure of the latter complex was established by IR, UV, and 1H and 31P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl3 with three equivalents of LiC5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3 gave the hexanuclear complex MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3. 相似文献
8.
9.
《Journal of organometallic chemistry》1987,330(3):415-428
The crystal and molecular structures of (η5-C5H5)Fe[η5--C5H4CCo3(CO)9] (1), Pna21, α 17.354, b 11.463, c 11.207 Å Z = 4, R = 0.053, Rw = 0.056 for 939 reflections (I>3σ(I)) at 293 K, and (η5-C5H5Fe[η5--C5H4CCo3(η5C5H5)3CH] (2), P21/n, a 13.807(9), b 11.254(4), c 13.991(9) Å, β 99.98(5)°, Z = 4, R = 0.033 and Rw = 0.033 for 3051 observed reflections (I>3σ(I)) at 180 K, have been determined by X-ray methods.The results provide a detailed characterisation of related tricobalt-carbon complexes directly bound to ferrocene residues. In 1 the ferrocenyl moiety tops the pyramidal CCo3 cluster core, while in 2 the CCo3C core is bipyramidal with a ferrocenyl substituent on one capping carbon atom and a hydrogen atom at the other. In both cases the ferrocenyl group is tilted towards one cobalt atom of the cluster core, a distortion believed to be the consequence of the non-degeneracy of the carbyne p(π) orbitals resulting from a cooperative π-interaction between the clusters and the ferrocenyl substituents. 相似文献
10.
Zhang Yongqiang Wang Baiquan Xu Shansheng Zhou Xiuzhong Sun Jie 《Transition Metal Chemistry》1999,24(6):722-725
Reactions of diiron complexes (E)[5-t-BuC5H3)Fe(CO)]2(-CO)2 [E = Me2Si (1), Me2SiSiMe2 (2), and Me2SiOSiMe2 (3)] with iodine in CHCl3 yielded diiodide complexes (E)[5-t-BuC5H3)Fe(CO)2I]2 [E=Me2Si (5), Me2SiSiMe2 (6), and Me2SiOSiMe2 (7)]. Like (1–3), complexes (5–7) also exists as mixtures of cis and trans isomers even though the Fe–Fe bond in (1–3) has been cleaved. When the pure isomers (1–3) reacted with iodine respectively in CHCl3, the cis isomers (1c–3c) yielded only the cis products (5c–7c), whereas the trans isomers (1t–3t) yielded only the trans isomers (5t–7t). This indicates that iodination of bridged diiron complexes is stereospecific. Similar treatment of trans-(Me2Si)[{5-t-(heptyl)C5H3}Fe(CO)]2(-CO)2 (4t) with iodine gave only the trans product (Me2Si)[{5-t-(heptyl)C5H3}Fe(CO)2I]2 (8t). The molecular structure of (5t) was determined by X-ray diffraction. 相似文献
11.
12.
《Journal of organometallic chemistry》1988,353(2):C23-C26
Mild, reductive carbonylation of (C5Me5)TaCl4 in the presence of trimethylphosphine gives (C5Me5)Ta(CO)4 in 47% yield. The intermediate (C5Me5)TaCl2- (CO)2(PMe3) has been isolated from the reaction of (C5Me5)TaCl2(PMe3)2 with carbon monoxide and its crystal structure determined (space group P212121). 相似文献
13.
《Journal of organometallic chemistry》2003,665(1-2):226-232
Photolysis of a benzene solution containing [Fe3(CO)9(μ3-E)2] (E=S, Se), [(η5-C5R5)Fe(CO)2(CCRI)] (R=H, Me; RI=Ph, Fc), H2O and Et3N results in formation of new metal clusters [(η5-C5R5)Fe3(CO)6(μ3-E)(μ3-ECCH2RI)] (R=H, RI=Ph, E=S 1 or Se 2; R=Me, RI=Ph, E=S 3 or Se 4; R=H, RI=Fc, E=S 5; R=Me, RI=Fc, E=S 6 or Se 7). Reaction of [Fe3(CO)9(μ3-S)2]with [(η5-C5R5)Mo(CO)3(CCPh)] (R=H, Me), under same conditions, produces mixed-metal clusters [(η5-C5R5)MoFe2(CO)6(μ3-S)(μ-SCCH2Ph)] (R=H 8; R=Me 9). Compounds 1–9 have been characterised by IR and 1H and 13C-NMR spectroscopy. Structures of 1, 5 and 9 have been established crystallographically. A common feature in all these products is the formation of new C-chalcogen bond to give rise to a (ECCH2RI) ligand. 相似文献
14.
《Journal of organometallic chemistry》1986,316(3):325-333
The protonated species [Fe2(η-C5H5)2(CO)2(η-CO){μ-CN(Me)H}]X, [Fe2(η-C5H5)2(CO)(CNMe)(μ-CO){μ-CN(Me)H}][X], and [Fe2(η-C5H5)2(CO)2{η-CN(Me)H}2][X]2 react with one equivalent of AgY. The Ag+ and one H+ act together as a two-electron oxidant. Silver metal is precipitated quantitatively and the substrates cleaved to give mono-nuclear products of the type (a) [Fe(η-C5H5)(CO)(L)X] and [Fe(η-C5H5(CO)(L)Y] or (b) Fe(η-C5H5(CO)(L)(CNMe)][X] (L = CO, CNMe). If X− and Y− are both coordinating anions such as NO3−, I−, or Br− or the solvent is MeCN products of type (a) are usually obtained with X = Y = MeCN+ if acetonitrile is used as the solvent. However, if either X− or Y− is a non-coordinating anion such as BF4− or PF6− and methanol is the solvent, the products are usually those of type (b). When X− = [p-MeC6H4SO3]−, both types of products are obtained in significant amounts. If two equivalents of Ph3P are added to the methanol solution of [Fe2(η-C5H5)2(CO)2{-CN(Me)H}2[BF6]2, no reaction takes place until the third equivalent of AgNO3 has been added. The products have been isolated and characterized by analysis and infrared spectroscopy. The previously unreported [Fe2(η-C5H5)2(CO)(CNMe)(η-CO){η-CN(Me)H}] X salts are described for X− = BF4−, PF6−, Br− · 2H2O, I− · H2O, NO3− · 0.5H2O, and p-MeC6H4SO3−. 相似文献
15.
《Journal of organometallic chemistry》1987,327(2):C33-C36
(η5-C5Me5)(CO)2(PPh3)MoCHO (2) one of the few isolated neutral metal formyls, reacts with the electrophilic reagents (CF3COOH and CH3SO3F without disproportionation to give the secondary carbene complexes [(η5-C5Me5)(CO)2(PPh3)Mo(CHOE)]+ X− (E = H, X = CF3COO (4); E = Me, X = PF6 (5)). 相似文献
16.
Zhang Yongqiang Wang Baiquan Xu Shansheng Zhou Xiuzhong 《Transition Metal Chemistry》1999,24(5):610-614
A series of bridged diruthenium complexes (E)[(5-C5H4)Ru(CO)]2(-CO)2 (E = Me2Ge (2); Me2SiOSiMe2 (3); Me2SiOSiMe2OSiMe2 (4)) has been prepared by reacting Ru3(CO)12 with Cp2E in refluxing heptane. The molecular structures of (2) and (4) have been determined by X-ray diffraction. 相似文献
17.
A. R. Kudinov V. I. Meshcheryakov P. V. Petrovskii M. I. Rybinskaya 《Russian Chemical Bulletin》1999,48(1):176-178
Compounds (η-C5R5)Fe[η-9-(Me2S)-7,8-C2B9H10] (R=H, Me) and (η-C4Me4)Co[η-9-(Me2S)-7,8-C2B9H10] were synthesized by the reactions of Na[9-(Me2S)-7,8-C2B9H10] with complexes [(η-C5H5)Fe(MeCN)3]PF6, [(η-C5Me5)Fe(MeCN)3]BF4, and [(η-C4Me4)Co(MeCN)3]PF6, respectively.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 177–179, January, 1999. 相似文献
18.
茂金属配合物[(eat5-C5H4R)Mo(CO)3 ]2(R: SiMe3 ,Si2Me5)的电子结构研究 总被引:3,自引:0,他引:3
运用G98W,采用Lanl2dz基组,对茂金属配合物[(eat5-C5H4R)Mo(CO)3]2 (R: SiMe3, Si2Me5)进行从头算研究,探讨配合物结构单元的稳定性、分子轨道能量、原子净电荷布居规律,以及一些前沿分子轨道的组成特征等,结果表明,标题配合物结构在能量上是稳定的,作为结构单元而存在. 相似文献
19.
《Journal of organometallic chemistry》1986,301(2):145-151
Ph3GeSiMe3 and Ph3GeSiMe2Fe(CO)2(η5-C5H5) have been synthesized and their crystal structures determined. The GeSi bond in iron (2.405(2) Å) is longer by 0.021 Å than in the simple germylsilane (2.384(1) Å). The significant shortening of the SiFe bond (2.328(1) Å) in the iron complex compared to that in the analogous Ph3SiSiMe2Fe(CO)2(η5-C5H5) (2.346(1) Å) and spectroscopic data indicate an enhanced SiFe interaction. 相似文献
20.
It was found that the 16-C6H5Cr(CO)3 ligand migrates into the cyclopentadienyl ring when the 5-C5H5(CO)2Fe 16-C6H5Cr(CO)3 binuclear complex is metallated with BunLi. Under the same conditions, no migration of the phenyl ligand in the 5-C5H5(CO)2Fe 1-C6H5 complex was observed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 325–326, February, 1994. 相似文献