Heteronuclear tungsten and cobalt derivatives of the 16-electron half-sandwich complex Cp*Rh[E2C2(B10H10)] (E = S, Se)

The 16-electron half-sandwich rhodium complex [Cp*Rh{E2C2(B10H10)}] [E = S (1a), Se (1b)] (Cp* = eta(5)-C5Me5) reacted with W(CO)(3)(py)(3) in the presence of BF3 center dot Et2O in THF solution to afford {Cp*Rh[E2C2(B10H10)]}(2)W(CO)(2) (E = S (2a); Se (2b)), (Cp*Rh)(2)[S2C2(B10H10)] (3), CP*Rh[S2C2(B10H10)]W(CO)(2)[S2C2(B10H10)] (4), and Cp*Rh(CO)[Se2C2(B10H10)]W(CO)(5) (5). The trinuclear clusters {Cp*Rh[E2C2(B10H10)}[CO2(CO)(5)] [E = S (6a), Se (6b)] were obtained from the reactions of 1a and 1b with CO2(CO)(8) in the presence of Me3NO. The complexes have been fully characterized by IR and NMR spectroscopy as well as by element analyses. The X-ray crystal structures of complexes 2-6 are reported.