The oxidative addition of Mel to the Ir(I) square-planar complex Irf(CO)((R)-(+)-BINAP) where (R)-(+)-BINAP = (R)-(+)-2,2'-bis(drphenylphosphino)-1,1'-binaphthyl)) results in the formation of two diastereomers in a 2:1 ratio of the Ir(III) oxidative addition product Irl(2)(CO)(Me)((R)-(+)-BINAP) (4a and 4b) in a 85% overall yield Upon iodide abstraction from the diastereomeric mixture with 2 equiv of AgSbF6 in the presence of diethyl isopropylidene malonate (DIM), two diastereomers of the dicationic complex [Ir(CO)(Me)(DIM)((R)-(+)-BINAP)][SbF6](2) (5) are formed in a 90% yield with a ratio of 9.1. One diastereomer of the diiodide complex 4 and one diastereomer of the dicationic complex 5 have been characterized by X-ray diffraction An anion exchange reaction of 5 with NaBAr4f- (BAr4f-= B(3,5-(CF3)(2)C6H3)(4)) affords [Ir(CO)(Me)(DIM)-((R)-(+)-BINAP)]BAr4f](2) (6) in quantitative yield Both 5 and 6 are active Lewis acid catalysts for the polarized Nazarov cyclization and the Drels-Alder reaction In the Nazarov cyclization, when NaBAr4f is added as a cofactor for the reaction catalyzed by 5 or 6, the resultant oxyallyl cation intermediate from the 4 pi conrotation undergoes a Wagner-Meerwein rearrangement to afford spirocyclic cyclopentenones in modest to good yields