Cobaltocene reductions of multiply bonded dirhenium complexes: isolation, characterization and reactivity studies of [(.eta.5-C5H5)2Co][Re2(O2CR)4Cl2], [(.eta.5-C5H5)2Co][Re2Cl6(PR3)2] and [(.eta.5-C5H5)2Co][Re2Cl5(PR3)3] Academic Article uri icon


  • The quadruply bonded dirhenium(III) complexes Re2Cl6(PR3)2 (PR3 = PEt3, P-n-Pr3, PMePh2, PEtPh2) and Re2(O2CR)4Cl2 (R = C3H7, CMe3, Ph) are reduced by cobaltocene in acetone to give the paramagnetic salts [(η5-C5H5)2Co] [Re2Cl6(PR3)2] and [(η5-C5H5)2Co] [Re2(O2CR)4Cl2], respectively, complexes which are derivatives of the Re25+ core. The cobaltocene reduction of Re2Cl5(PMePh2)3 to give [(η5-C5H5)2Co][Re2Cl5(PMePh2)3] and its oxidation to [Re2Cl5(PMePh2)3]PF6 by NO+PF6- have also been accomplished. These results demonstrate that mixed halide-phosphine complexes of Re2n+ (n = 6, 5, 4) exhibit the most extensive redox chemistry of any class of multiply bonded dimetal species. The nonredox substitution chemistry of [Re2Cl6(PR3)2]- with PR3 and of [Re2Cl5(PR3)3]- with PR3 has been shown to lead to the formation of Re2Cl5(PR3)3 and Re2Cl4(PR3)4, respectively. © 1985, American Chemical Society. All rights reserved.

author list (cited authors)

  • Dunbar, K. R., & Walton, R. A.

citation count

  • 20

publication date

  • January 1985