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异双金属钌/铂和钼/铂配合物的合成与电化学

Synthesis and Electrochemistry of Heterobimetallic Ruthenium/Platinum and Molybdenum/Platinum Complexes.

作者信息

Orth Stephen D., Terry Michael R., Abboud Khalil A., Dodson Brian, McElwee-White Lisa

机构信息

Department of Chemistry, University of Florida, Gainesville, Florida 32611.

出版信息

Inorg Chem. 1996 Feb 14;35(4):916-922. doi: 10.1021/ic9510977.

DOI:10.1021/ic9510977
PMID:11666265
Abstract

As starting materials for heterobimetallic complexes, [RuCp(PPh(3))CO(PPh(2)H)]PF(6) and [RuCp(PPh(3))CO(eta(1)-dppm)]PF(6) were prepared from RuCp(PPh(3))(CO)Cl. In the course of preparing [RuCp(eta(2)-dppm)(eta(1)-dppm)]Cl from RuCp(Ph(3)P)(eta(1)-dppm)Cl, the new monomer RuCpCl(eta(1)-dppm)(2) was isolated. The uncommon coordination mode of the two monodentate bis(phosphines) was confirmed by X-ray crystallography [a = 11.490(1) Å, b = 14.869(2) Å, c = 15.447(2) Å, alpha = 84.63(1) degrees, beta = 70.55(1) degrees, gamma = 72.92(1) degrees, V = 2378.7(5) Å(3), d(calc) = 1.355 g cm(-)(3) (298 K), triclinic, P&onemacr;, Z = 2]. The dppm-bridged bimetallic complexes RuCp(PPh(3))Cl(&mgr;-dppm)PtCl(2), RuCpCl(&mgr;-dppm)(2)PtCl(2), and [RuCp(PPh(3))CO(&mgr;-dppm)PtCl(2)]PF(6) each exhibit electrochemistry consistent with varying degrees of metal-metal interaction. The cationic heterobimetallic complexes [Mo(CO)(3)(&mgr;-dppm)(2)Pt(H)]PF(6) and [MoCp(CO)(2)(&mgr;-PPh(2))(&mgr;-H)Pt(PPh(3))(MeCN)]PF(6) were prepared by chloride abstraction from the corresponding neutral bimetallic species and show electrochemical behavior similar to the analogous Ru/Pt complexes.

摘要

作为异双金属配合物的起始原料，[RuCp(PPh(3))CO(PPh(2)H)]PF(6)和[RuCp(PPh(3))CO(η(1)-dppm)]PF(6)由RuCp(PPh(3))(CO)Cl制备。在由RuCp(Ph(3)P)(η(1)-dppm)Cl制备[RuCp(η(2)-dppm)(η(1)-dppm)]Cl的过程中，分离出了新的单体RuCpCl(η(1)-dppm)(2)。通过X射线晶体学确定了两个单齿双膦的罕见配位模式[a = 11.490(1) Å，b = 14.869(2) Å，c = 15.447(2) Å，α = 84.63(1)°，β = 70.55(1)°，γ = 72.92(1)°，V = 2378.7(5) Å(3)，d(calc) = 1.355 g cm(-)(3) (298 K)，三斜晶系，P&onemacr;，Z = 2]。dppm桥联的双金属配合物RuCp(PPh(3))Cl(μ-dppm)PtCl(2)、RuCpCl(μ-dppm)(2)PtCl(2)和[RuCp(PPh(3))CO(μ-dppm)PtCl(2)]PF(6)各自表现出与不同程度的金属-金属相互作用相一致的电化学性质。阳离子异双金属配合物[Mo(CO)(3)(μ-dppm)(2)Pt(H)]PF(6)和[MoCp(CO)(2)(μ-PPh(2))(μ-H)Pt(PPh(3))(MeCN)]PF(6)通过从相应的中性双金属物种中提取氯离子制备，并且表现出与类似的Ru/Pt配合物相似的电化学行为。

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