Reactivity of rhodium and iridium peroxido complexes towards hydrogen in the presence of B (C6F5) 3 or H (OEt2) 2B3, 5- (CF3) 2C6H34

The peroxido complexes trans-M (4-C5F4N) (O2) (CNtBu) (PR3) 2 (1: M = Rh, R = Et; 2a: M = Ir, R = iPr) can be used in the metal-mediated hydrogenation of O2. The reaction of trans-Rh (4-C5F4N) (O2) (CNtBu) (PEt3) 2 (1) with B (C6F5) 3 and H2 gave trans-Rh (4-C5F4N) (CNtBu) (PEt3) 2 (3), OPEt3 and (H2O) ·B (C6F5) 3, whereas treatment of H (OEt2) 2B3, 5- (CF3) 2C6H34 with 1 in the presence of H2 yielded trans-Rh (4-C5F4N) (CNtBu) (PEt3) 2 (3) and H2O2. The reactivity of 2a towards B (C6F5) 3 and BClCy2 was also studied and an intermediate was detected which is assigned to be trans-Ir (4-C5F4N) (Cl) (OOBCy2) (CNtBu) (PiPr3) 2 (4a).