Hydride addition to and reduction of Cp★Ir(η6-BT)2+ and Cp★Ir(η6-DBT)2+, where BT  benzo[b]thiophene and DBT  dibenzothiophene

Abstract

Abstract The benzo[b]thiophene (BT) complexes Cp★Ir(η 6 -BTs) 2+ , where BTs is BT ( 1a ), 2-MeBT ( 1b ), 3-MeBT ( 1c ) or 2,3-Me 2 BT ( 1d ), react with H 2 Al(OCH 2 CH 2 OMe) 2 − to add two H − to the coordinated arene ring of the BTs to give the cyclohexadiene complexes Cp★Ir(η 4 -BTs·2H), 2a–d . The dibenzothiophene complex Cp★Ir(η 6 -DBT) 2+ ( 3 ) reacts similarly to give Cp★Ir(η 4 -DBT·.2H) ( 4 ). Both of these reactions can be reversed by adding Ph 3 C + . Two-electron reductions of 1c and 3 give the η 4 -arene complexes Cp★Ir(η 4 -3-MeBT) ( 5 ) and Cp★Ir(η 4 -DBT) ( 6 ). Compounds 2c and 4 have been characterized by X-ray diffraction.