Coordination and oxidative addition at a low-coordinate rhodium(I) beta-diiminate centre

The reaction of 14e L(Me)Rh(coe)] (1; L(Me)double bond]ArNC(Me)CHC(Me)NAr, Ardouble bond]2,6-Me(2)C(6)H(3); coedouble bond]cis-cyclooctene) with phenyl halides and thiophenes was studied to assess the competition between sigma coordination, arene pi coordination and oxidative addition of a C-X bond. Whereas oxidative addition of the C-Cl and C-Br bonds of chlorobenzene and bromobenzene to L(Me)Rh results in the dinuclear species L(Me)Rh(Ph)(micro-X)](2)] (X=Cl, Br), fluorobenzene yields the dinuclear inverse sandwich complex L(Me)Rh](2)(anti-micro-eta(4):eta(4)-PhF)]. Thiophene undergoes oxidative addition of the C-S bond to give a dinuclear product. The reaction of 1 with dibenzob,d]thiophene (dbt) in the ratio 1:2 resulted in the formation of the sigma complex L(Me)Rh(eta(1)-(S)-dbt)(2)], which in solution dissociates into free dbt and a mixture of the mononuclear complex L(Me)Rh(eta(4)-(1,2,3,4)-dbt)] and the dinuclear complex L(Me)Rh](2)(micro-eta(4)-(1,2,3,4):eta(4)-(6,7,8,9)-dbt)]. The latter could be obtained selectively by the 2:1 reaction of 1 and dbt. Reaction of 1 with diethyl sulfide produces L(Me)Rh(Et(2)S)(2)], which in the presence of hydrogen loses a diethyl sulfide ligand to give L(Me)Rh(Et(2)S)(H(2))] and catalyses the hydrogenation of cyclooctene.