Formation of Cup-Shaped Metallic Clusters via B−H Activation at the B(3)/B(6) Site of anortho-Carborane-1,2-dichalcogenolato Ligand

Dimetallic complexes {Cp*Ir[E 2 C 2 (B 9 H 9 )][(cod)Ir(OCH 3 )]} (E = S, 3a; E = Se, 3b ) and {Cp * Ir[E 2 C 2 (B 10 H 9 )][(cod)Ir]} (E = S, 4a; E = Se, 4b ) were synthesized by the reaction of half-sandwich complexes Cp*Ir[E 2 C 2 (B 10 H 10 )] (E = S, 1a; Se, 1b ) with 2 equiv of [Ir(cod)(μ-OMe)] 2 ( 2-Ir ). Analogous reactions of 1a with [Rh(cod)(μ-OMe)] 2 ( 2-Rh ) were investigated, and three complexes, {Cp*Ir[S 2 C 2 (B 9 H 9 )][(cod)Rh(OCH 3 )]} ( 5a ), {Cp*Ir[S 2 C 2 (B 10 H 10 )][(cod)Rh]} ( 6a ), and {Cp*Ir[S 2 C 2 (B 10 H 9 )][(cod)Rh]} ( 7a ), were obtained. By comparing the two reactions, the routes of metal-induced B−H activation at B(3)/B(6) of the ortho -carborane-1,2-dichalcogenolato ligand were investigated. These nido- carborane complexes such as 3a, 3b, and 5a contain intercluster metal−metal bonds. Moreover, the V-shaped trimetallic units {(cod)Ir[E 2 C 2 (B 9 H 8 )][(cod)Ir(OCH 3 )][(C 8 H 13 )Ir]} (E = S, 9a; Se, 9b ) have been constructed through the M 2 - nido -carborane complexes {(cod)Ir[E 2 C 2 (B 9 H 9 )][(cod)Ir(OCH 3 )]} (E = S, 8a; Se, 8b ). Complexes 3 − 10 were characterized by NMR spectroscopy ( 1 H, 11 B NMR), and X-ray structural analyses were reported for complexes 3a, 3b, 4a, 5a, 6a, 8a, 9b, and 10b .