New synthetic pathway to mono- and bis-indenyl complexes of molybdenum(IV)

The complex IndMoCl(3)(CO)(2) (Ind = eta(5)-C9H7) has been synthesized by the reaction of IndMo-(eta(3)-C3H5)(CO)(2) with HCl gas in dichloromethane at 25 degrees C. Thermal decarbonylation of IndMoCl(3)(CO)(2) in chloroform gives paramagnetic IndMoCl(3) (mu(eff) = 1.48 mu(B)). A consistent stepwise route to bis-indenyl derivatives of molybdenum is available upon treatment of IndMoCl(3)(CO)(2) with Kind in THF at low temperature. The complex IndMo(eta(3)-Ind)(CO)(2) is obtained in high yield and opens a convenient entry into bis-indenyl molybdenum chemistry. The reaction of IndMo(eta(3)-Ind)(CO)(2) with Ph3CBF4, in CH2Cl2, yields [Ind(2)Mo(CO)(2)][BF4](2). Solvolysis of [Ind(2)Mo(CO)(2)][BF4](2) in acetonitrile affords [Ind(2)Mo(CO)(NCMe)][BF4](2) and [Ind(2)-Mo(NCMe)(2)][BF4](2). The reaction of [Ind(2)Mo(NCMe)(2)][BF4](2) with [Bu4N][S2CNEt2] forms the dithiocarbamate complex [Ind(2)Mo(S2CNEt2)][BF4]. The molecular structures of IndMo(eta(3)-Ind)(CO)(2) and [Ind(2)Mo(S2CNEt2)][BF4] have been determined by single-crystal X-ray diffraction.