三苯膦铁硫原子簇配合物(μ-cy-C~6H~11S)(μ-n-C~5H~11S)Fe~2(CO)~5PPb~3的合成和晶体结构

通过(μ-cy-C~6H~11S)(μ-n-C~5H~11S)Fe~2(CO)~6同PPh~3在苯中,SO℃下反应5小时,制得了三苯膦单取代产物(μ-cy-C~6H~11S)(μ-n-C~5H~11S)Fe~2(CO)~5PPh~3(1).并用X衍射技术测得其单晶结构.晶体属正交晶系,空间群为Pbca,a=12.940(2)A,b=23.170(7)A,c=23.294(2)A,Do=1.25g.cm^-^3.Z=8.采用直接法(RANTAN)测得其初结构,以SHELX-76程序经全矩阵最小二乘法分块修正,最后偏离因子R=0.043,Rw-0.058.单晶X射线分析表明,三苯膦取代反应发生在配合物Fe-Fe键的反位上;两个硫桥以不等性方式同两个铁原子相连;硫桥上的取代基cy-C~6H~11及n-C~5H~11同处于e,e键,且弯向Fe~2原子一边.重要的键长有Fe(1)-Fe(2)=2.527(1)A,Fe(1)-S=2,287(1)及2.281(1)A,Fe(1)-P=2.271(1)A,Fe(2)-S=2.267(1)及2.275(1)A.五个Fe-C键在1.757(7)～1.810(6)A范围内。     

Synthesis of a transition metal-dithionite complex, (η5-C5H5)(CO)2FeS(O)2S(O)2Fe(CO)2(η5-C5H5)

The reaction of Na[η⁵-C₅H₅Fe(CO)₂] with large excess of SO₂ in THF at ?78°C followed by warming to room temperature affords an iron—dithionite complex, (η⁵-C₅H₅)(CO)₂FeS(O)₂S(O)₂Fe(CO)₂(η⁵-C₅H₅).     

Synthesis and Crystal Structure of Cluster 〔C_6H_4-1,2-(CO_2CH_2C_2H-μ)_2〕〔Co_2(CO)_6〕_2

１ＩＮＴＲＯＤＵＣＴＩＯＮＯｃｔａｃａｒｂｏｎｙｌｄｉｃｏｂａｌｔｉｓａｖｅｒｙｃｏｎｖｅｎｉｅｎｔｓｔａｒｔｉｎｇｍａｔｅｒｉａｌｆｏｒｔｈｅｐｒｅｐａｒａｔｉｏｎｏｆａｌｍｏｓｔａｎｙｃｏｂａｌｔｃｏｍｐｏｕｎｄ〔１〕．Ｔｈｅｒｅａｃｔｉｏｎｓｏ...     

Crystal and molecular structure of (μ-p-CH3C6H4C2S) (μ-n-C3H7S)Fe2(CO)6Co2(CO)6

The crystal and molecular structure of the complex containing cobalt-carbon and iron-sulfur cluster cores, (μ-p-CH₃C₆H₄C₂S) (μ-n-C₃H₇S)Fe₂(CO)₆Co₂(CO)₆, has been determined by X-ray diffraction method. The crystals are triclinic, space group P&1bar;, with a — 9.139(2), b=9.610(1), c-17.183(2) Å, α = 84.36(1), β-89.45(1), γ=88.15(1)°, V-1501.0 ų; Z=2, D_c=1.74 g/cm³. R=0.072, Rw=0.081. The results of the structure determination show a cobalt-carbon cluster core formed through the reaction of (μ-p-CH₃C₆H₄C₂S)(μ-n-C₃H₇S)Fe₂(CO)₆ with Co₂(CO)₈. In the cobalt-carbon cluster core, the bond length of the original C≡C lengthened to 1.324 Å which is close to the typical value of carbon-carbon double bond. The groups connecting the carbons of the cluster core are in cis position and lie on the opposite side of cobalt atoms. In this complex, the conformation of —SC₃H₇ is e-type, while that of —SC₂C₆H₄CH₃ is a-type.     

Synthesis of clusters Fe2(CO)6(μ-XCH2CH=CH2)(μ3-X)Fe(CO)2Cp (X = Se, S; Cp = η5-C5H5)

The clusters Fe₂(CO)₆(μ-XCH₂CH=CH₂)(μ₃-X)Fe(CO)₂Cp (X = S, Se) were prepared by the successive treatment of the bi- and trimetallic complexes Fe₂(CO)₆(μ-Se₂) and Fe₃(CO)₉(μ₃-X) with allylmagnesium chloride and CpFe(CO)₂I. The clusters obtained contain a noncoordinated C=C bond. The structure of the Se-containing cluster was suggested on the basis of comparison of its spectral data (IR,¹H NMR, and Mössbauer spectra) with the spectra of the analogous S-containing complex, which was previously characterized by X-ray diffraction analysis.     

Synthesis,Structure, and Redox Properties of [{(η5-C5H5)Co(S2C6H4)}2Mo(CO)2], a Novel Metalladithiolene Cluster

Metal–metal bond formation by a cobaltadithiolene complex was observed for the first time in the reaction of [Co(η⁵-C₅H₅)(S₂C₆H₄)] with [Mo(CO)₃(py)₃] and BF₃ to give the Co-Mo-Co cluster 1 . Cyclic voltammetry reveals that 1 undergoes two one-electron reduction steps at the Co centers, which is indicative of transmission of the Co−Co electronic interaction through the Mo center.     

Co[(C6H11O)2PS2]2·2Py的合成和晶体结构

二烃基二硫代磷酸酯及其过渡金属配合物能阻止烃类自动氧化,是一种很重要的抗氧、抗磨广泛应用于石油的添加剂、高分子材料的稳定剂和人造橡胶的硫化促进剂[1,2].在生物学上也具有十分重要的地位,具有杀虫、抗菌、抗癌和抑制酶水解等特性[3].因此,对该领域的研究也十分活跃.对二烃基二硫代磷酸酯合过渡金属配合物及其加合物的研究,游效曾等已作过多次报导[4-16].     

混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构研究

本文用电化学方法和X射线单晶结构分析, 研究了混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构, 由循环伏安结果, 分别讨论了簇合物中(C5H5FeC5H4和C2O2中心的成键性质, X射线单晶结构分析表明: 晶体属单斜晶系, 空间群为P21, 晶胞参数a=11.845(6), b=8.155(6), c=24.031(6)A, β=90.88°,晶胞中分子数Z=4, 密度Do=1.637g.cm^-^2, 分析了(C5H5FeC5H4C2Ph)Co2(CO)6的结构特点, 并从成键角度讨论了(RC2R^1)Co(CO)6类簇合物的结构随RC2R^1不同而变化的规律。     

Beiträge zur Chemie des Phosphors. 67. Zur Kenntnis der Cyclotriphosphane (PC6H5)3, (PC6H5)2(PC2H5) und (PC6H5)2(PCH3)

Contributions to the Chemistry of Phosphorus. 67. About the Cyclotriphosphanes (PC₆H₅)₃, (PC₆H₅)₂(PC₂H₅), and (PC₆H₅)₂(PCH₃) The reaction of (CH₃)₃Si(C₆H₅)P? P(C₆H₅)Si(CH₃)₃ with RPCl₂ (R = C₆H₅, C₂H₅, CH₃) yields the cyclotriphosphanes (PC₆H₅)₃ 1 , (PC₆H₅)₂(PC₂H₅) 3 , and (PC₆H₅)₂(PCH₃) 4 , respectively. Besides, the corresponding homo- and mixed-substituted cyclotetraphosphanes, cyclopentaphosphanes, and cyclohexaphosphanes are formed. The relative concentrations of the cyclotriphosphanes in the reaction mixtures decrease continuously, whereas those of the cyclopentaphosphanes increase. The reasons for these ring-interconversion reactions of the cyclophosphanes (PR)_n are discussed. The cyclotriphosphanes 1, 3 , and 4 are characterized by ³¹P chemical shifts between +130 and +160 ppm that are at considerable high field compared to open-chain triphosphanes and cyclophosphanes of different ring-size. The substituents R are situated on both sides of the P₃-ring plane, thus giving rise to two diastereomers of 3 that are observed simultaneously in the statistically expected ratio. The ³¹P n.m.r. parameters of 1 and 3 are reported and discussed.     

Synthesis and Crystal Structure of [(n5-C5Me5)2Fe2S4](PF6)2

Abstract

The title compound was synthesized by electrochemical oxidation of (η⁵-C₅Me₅)₂Fe₂S₄ and its X-ray crystal structure was determined. A μ₂-S₂ ligand is converted to μ₂-η²-s₂ ligand by the oxidation.     

Photochemical reactions of (CO)2 (PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3

Conclusions The photochemical reactions of (CO)₂(PPh₃)MnC₅H₄Fe(CO)₂C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)₂C₅H₅ with PPh₃ gave the products of replacing the CO on the Fe atom by PPh₃: respectively (CO)₂(PPh₃)MnC₅H₄Fe (CO)(PPh₃)C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)(PPh₃)C₅H₅.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.     

Synthesis and Crystal Structure of (CO)5ReSnMe2Re(CO)5

１ＩＮＴＲＯＤＵＣＴＩＯＮＨｏｍｏ ｄｉｎｕｃｌｅａｒｍｅｔａｌｃａｒｂｏｎｙｌｃｌｕｓｔｅｒｓｈａｖｅｂｅｎｓｔｕｄｉｅｄｗｉｄｅｌｙｆｏｒｔｈｅｉｒｎｏｖｅｌｓｔｒｕｃｔｕｒｅｓａｎｄｕｓｅｓｉｎｏｒｇａｎｉｃｓｙｎｔｈｅｓｉｓ〔１〕．Ｅｘａｍｐ...