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1.
Maryam Rahimi Reza Ghiasi Jamaat Parisa Rajabali 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2020,94(1):125-133
Russian Journal of Physical Chemistry A - This study investigates the effect of different substituents on the isomerization reaction of the [(η5‑C5H5)(CO)(Me)Re≡CC6H5] carbyne... 相似文献
2.
《Polyhedron》1988,7(8):623-628
Reactions of [(η5-C5H5)RuCl(AsPh3)2] with the ligands of the type RCSNHCOOC2H5 (R = 4-toluene, 2-pyrrole, 1-pyrrole, 2-thiophene), R1CSNHCOOR2 (R1 = 2-pyrrole, R2 = NH2, NHPh) and 2-thiopyrrole-1,2-dicarboximide, lead to the formation of diamagnetic compounds of the formula [(η5-C5H5)RuCl(AsPh3)(LH)] · xCH2Cl2 (x = 0 or 1/2). These compounds and spectroscopic (UV, Vis, IR, and 1H NMR) data are reported. A distorted octahedral geometry is proposed for the complexes. 相似文献
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A. R. Kudinov A. A. Fil'chikov P. V. Petrovskii M. I. Rybinskaya 《Russian Chemical Bulletin》1999,48(7):1352-1355
The parent 30-electron triple-decker iron complex with cyclopentadienyl ligands, [(η-C5H5)Fe(μ-η:η-C5H5)Fe(η-C5H5)]PF6 (1), was prepared for the first time by visible-light irradiation of ferrocene and [(η-C5H5)Fe(η-C6H6)]PF6 in CH2Cl2 at 0 °C. An analogous reaction performed with the use of (η-C5H5)Co(η-C4Me4) (2) instead of ferrocene afforded the thermally labile 30-electron cationic iron-cobalt triple-decker complex [(η-C5H5)Fe(μ-η:η-C5H5)Co(η-C4Me4)]PF6. The latter reacted with compound 2 at 20 °C to form the symmetrical 30-electron cationic dicobalt triple-decker complex
[(η-C4Me4)Co(μ-η:η-C5H5)Co(η-C4Me4)] PF6.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 7, pp. 1364–1367, July, 1999. 相似文献
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7.
《Journal of organometallic chemistry》1994,481(1):69-73
In the symmetrical crystal structure of [{U(η5-C4Me4P)(μ-η5,η1-C4Me4P)(BH4)}2], the U-P bond distances for the terminal and bridging η5-phospholyl ligands are 2.945(3) and 2.995(3) Å respectively, and the U-P (η1-phospholyl) bond length is equal to 2.996(3) Å; the tridentate borohydride ligands are cis to the (UP)2 ring. The cis and trans isomers of [{U(Cp1)(μ-η5,η1C4 Me4P)(BH4)}2] (Cp1 = η5-C5Me5) are in equilibrium in toluene. 相似文献
8.
Pandey KK 《The journal of physical chemistry. A》2011,115(30):8578-8585
Density functional theory calculations have been performed for the dimethylgallyl complexes of iron, ruthenium, and osmium [(η(5)-C(5)H(5))(L)(2)M(GaMe(2)] (M = Fe, Ru, Os; L = CO, PMe(3)) at the DFT/BP86/TZ2P/ZORA level of theory. The calculated geometry of the iron complex [(η(5)-C(5)H(5))(CO)(2)Fe(GaMe(2))] is in excellent agreement with structurally characterized complex [(η(5)-C(5)H(5))(CO)(2)Fe(Ga(t)Bu(2))]. The Pauling bond order of the optimized structures shows that the M-Ga bonds in these complexes are nearly M-Ga single bond. Upon going from M = Fe to M = Os, the calculated M-Ga bond distance increases, while on substitution of the CO ligand by PMe(3), the calculated M-Ga bond distances decrease. The π-bonding component of the total orbital contribution is significantly smaller than that of σ-bonding. Thus, in these complexes the GaX(2) ligand behaves predominantly as a σ-donor. The contributions of the electrostatic interaction terms ΔE(elstat) are significantly smaller in all gallyl complexes than the covalent bonding ΔE(orb) term. The absolute values of the ΔE(Pauli), ΔE(int), and ΔE(elstat) contributions to the M-Ga bonds increases in both sets of complexes via the order Fe < Ru < Os. The Ga-C(CO) and Ga-P bond distances are smaller than the sum of van der Waal radii and, thus, suggest the presence of weak intermolecular Ga-C(CO) and Ga-P interactions. 相似文献
9.
《Journal of organometallic chemistry》1987,320(2):C19-C22
The complex [(η5-C5H5)Fe(CO)(PPh3)CH2CH3] is shown by 1H NMR spectroscopy and an X-ray crystal structure analysis to adopt a single conformation with the methyl group residing between the cyclopentadienyl and carbon monoxide ligands. 相似文献
10.
《Journal of organometallic chemistry》1991,402(3):C56-C58
Complete self-recognition of chirality is observed in the Michael addition of the enolate derived from R,S-[η5-C5H5Fe(CO)(PPh3-COCH3] to the acryloyl complex R,S-[(η5-C5H5Fe(CO)(PPh3)-COCHCH2)] to generate exclusively the single diastereoisomer of the glutaroyl complex RR,SS-[(η5-C5H5)Fe(CO)(PPh3)COCH2]2CH2. 相似文献
11.
Linear correlations between 13C NMR chemical shifts of unsubstituted terminal carbon atom of the allylic ligand in [(1-R-η3-C3H4)PdCl]2 and Na[(1-R-η3-C3H4)PdCl2] and the modified Hammett constants were established. Two-parameter correlations using the Swain-Lupton parameters R
+, R
−, and F were obtained.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1171–1174, June, 2008. 相似文献
12.
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
13.
《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
14.
《Polyhedron》1999,18(20):2583-2595
The reaction of the novel ferrocenyl Schiff base: [(η5-C5H5)Fe{(η5-C5H4)-CH=N-(C6H4-2-C6H5)}] (1) with Na2[PdCl4] and Na(CH3COO)·3H2O in a 1:1:1 molar ratio in methanol is reported. In this reaction two different di-μ-chloro-bridged cyclopalladated complexes: [Pd{[(η5-C5H3)-CH=N-(C6H4-2-C6H5)]Fe(η5-C5H5)}(μ-Cl)]2 (2a) and [Pd{[(C6H4-2-C6H4)-N=CH-(η5-C5H4)]Fe(η5-C5H5)}(μ-Cl)]2 (2b) can be formed depending on the experimental conditions. Compounds 2a and 2b, which differ in the nature of the metallated carbon atom (Csp2,ferrocene or Csp2,biphenyl, respectively), undergo cleavage of the ‘Pd(μ-Cl)2Pd’ bridges in the presence of thallium (I) acetylacetonate, deuterated pyridine or triphenylphosphine giving the monomeric derivatives: [Pd(C∧N)(acac)] (3a, 3b) and [Pd(C∧N)Cl(L)] {with L=py- d5(4a, 4b), PPh3(5a, 5b)}. The reactions of 2 with 1,2-bis(diphenylphosphino)ethane (dppe) reveal that the two isomers (2a and 2b) exhibit different reactivity versus dppe. These results have been interpreted on the basis of steric effects. 相似文献
15.
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
16.
Anagha Haridas Suvam Saha Shantabh Bedajna Prof. Dr. Sundargopal Ghosh 《欧洲无机化学杂志》2023,26(27):e202300312
Azametallacyclopropane-containing base stabilized borane complexes of group 5 transition metals have been synthesized and their structural aspects have been described. Treatment of Cp* based Ta and Nb chlorides, Cp*TaCl4 and Cp*NbCl4 with [LiBH4 ⋅ THF] followed by addition of ligands, such as 2-mercaptobenzothiazole, MBT, (C7H5NS2) and 2-mercaptobenzoxazole, MBO (C7H5NSO) led to the formation of complexes [Cp*M-[BHS(CH2ENC6H4)(C7H4NSE)] ( 1 : M=Ta, E=S; 2 ; M=Nb, E=S; 3 : M=Ta, E=O; 4 ; M=Nb, E=O, Cp*=pentamethyl-η5-cyclopentadienyl). By means of UV-vis absorption spectra, the electronic properties of these complexes associated with central metal atoms and heteroatoms (S or O) have been evaluated. In contrast, treatment of Cp*TaCl4 with 2-mercaptopyridine, MP, (C5H5NS) under the same reaction conditions yielded the agostic σ-borane Ta complex, [Cp*Ta(H3BNC5H4) (C5H4NS)(η2-S2)], 5 . Unlike 1 – 4 , where the metals interact with boron through bridging sulphur, 5 shows a notable σ-B−H bond interaction with Ta. All spectroscopic data of 1 – 5 along with the X-ray diffraction studies suggest complexes 2 , 4 , and 5 are base (amine) stabilized borane species. Computational studies based on Density Functional Theory (DFT) also supported this conclusion. 相似文献
17.
《Comptes Rendus Chimie》2002,5(4):319-324
The ligand substitution by diphosphine L–L on (η5-C5H5)Fe(CO)2I usually results in the chelated 〚(η5-C5H5)Fe(CO)(η2-L–L)+〛〚I–〛 product exclusively. One could suppress the chelated complexes and selectively prepare the bridged 〚{(η5-C5H5)Fe(CO)2}2(μ-L–L)2+〛 complexes by application of the electron-transfer chain catalysis with a chemical initiation. Introducing a catalytic amount of reductant at low temperature to the mixture of 2:1 (η5-C5H5)Fe(CO)2I/L–L in THF selectively produces the bridged complexes in 78–93% isolated yields where L–L is Ph2P(CH2)nPPh2, n = 1–4, or (η5-C5H4PPh2)2Fe. 相似文献
18.
《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
19.
《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
20.
《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