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

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-1κC2κN)-fac-Re(I)(bipy)(CO)(3)][PF(6)] (3) and [cis-Re(V)O(acac(2)pn)(µ-CN-1κC2κN)-fac-Re(I)(bipy)(CO)(3)][PF(6)] (4), respectively.