混合氧化态氰桥联 Re(V)氧代（acac(2)en/pn）和 Re(I)(bipy)(CO)3 配合物的研究。

Investigation of mixed oxidation state cyanide-bridged Re(V)oxo (acac(2)en/pn) and Re(I)(bipy)(CO)3 complexes.

机构信息

Department of Chemistry, Washington State University, P.O. Box 644630, Pullman, Washington 99164-4630, USA.

出版信息

Inorg Chem. 2011 Jun 6;50(11):4686-8. doi: 10.1021/ic2005002. Epub 2011 May 2.

DOI:10.1021/ic2005002

Abstract

A series of cyanide-bridged complexes that combine a low-valent photoacceptor rhenium(I) metal center with an electroactive midvalent rhenium(V) complex were prepared. The synthesis involved the preparation of novel asymmetric rhenium(V) oxo compounds, cis-Re(V)O(CN)(acac(2)en) (1) and cis-Re(V)O(CN)(acac(2)pn) (2), formed by reacting trans-[Re(V)O(OH(2))(acac(2)en)]Cl or trans-Re(V)O(acac(2)pn)Cl with [NBu(4)][CN]. The μ-bridged cyanide mixed-oxidation Re(V)-Re(I) complexes were prepared by incubating the asymmetric complexes, 1 or 2, with fac-[Re(I)(bipy)(CO)(3)][OTf] to yield cis-[Re(V)O(acac(2)en)(μ-CN-1κC:2κN)-fac-Re(I)(bipy)(CO)(3)][PF(6)] (3) and [cis-Re(V)O(acac(2)pn)(μ-CN-1κC:2κN)-fac-Re(I)(bipy)(CO)(3)][PF(6)] (4), respectively.

摘要

一系列氰桥接的配合物，将低价光受体铼（I）金属中心与电活性的中价铼（V）配合物结合在一起。合成涉及新型不对称铼（V）氧配合物的制备，cis-Re(V)O(CN)(acac(2)en)（1）和 cis-Re(V)O(CN)(acac(2)pn)（2），由 trans-[Re(V)O(OH(2))(acac(2)en)]Cl 或 trans-Re(V)O(acac(2)pn)Cl 与 [NBu(4)][CN] 反应形成。μ-桥接的氰化物混合氧化 Re(V)-Re(I) 配合物通过孵育不对称配合物 1 或 2 与 fac-[Re(I)(bipy)(CO)(3)][OTf] 来制备，得到 cis-[Re(V)O(acac(2)en)(μ-CN-1κC:2κN)-fac-Re(I)(bipy)(CO)(3)][PF(6)]（3）和 [cis-Re(V)O(acac(2)pn)(μ-CN-1κC:2κN)-fac-Re(I)(bipy)(CO)(3)][PF(6)]（4）。