Transition Metal Complexes of Cr, Mo, W and Mn Containing η1(S)-2,5-Dimethylthiophene, Benzothiophene and Dibenzothiophene Ligands

Abstract

The UV photolysis of hexanes solutions containing the complexes M(CO){sub 6} (M=Cr, Mo, W) or CpMn(CO){sub 3} (Cp={eta}{sup 5}-C{sub 5}H{sub 5}) and excess thiophene (T{sup *}) (T{sup *}=2,5-dimethylthiophene (2,5-Me{sub 2}T), benzothiophene (BT), and dibenzothiophene (DBT)) produces the {eta}{sup 1}(S)-T{sup *} complexes (CO){sub 5}M({eta}{sup 1}(S)-T{sup *}) 1-8 or Cp(CO){sub 2}Mn({eta}{sup 1}(S)-T{sup *})9-11, respectively. However, when T{sup *}=DBT, and M=Mo, a mixture of two products result which includes the {eta}{sup 1}(S)-DBT complex (CO){sub 5}Mo({eta}{sup 1}(S)-DBT) 4a and the unexpected {pi}-complex (CO){sub 3}Mo({eta}{sup 6}-DBT) 4b as detected by {sup 1}H NMR. The liability of the {eta}{sup 1}(S)-T{sup *} ligands is illustrated by the rapid displacement of DBT in the complex (CO){sub 5}W({eta}{sup 1}(S)-DBT) (1) by THF, and also in the complexes (CO){sub 5}Cr({eta}{sup 1}(S)-DBT) (5) and CpMn(CO){sub 2}({eta}{sup 1}(S)-DBT) (9) by CO (1 atm) at room temperature. Complexes 1-11 have been characterized spectroscopically ({sup 1}H NMR, IR) and when possible isolated as analytically pure solids (elemental analysis, EIMS). Single crystal, X-ray structural determinations are reported for (CO){sub 5}W({eta}{sup 1}(S)-DBT) and Cp(CO){sub 2}Mn({eta}{sup 1}(S)-DBT).