The novel phosphinine-based coordination compound [Cp*Ir- (P∧C)(CH3CN)]CF3SO3 (P∧C = cyclometalated 2,4,6-triphenylphosphinine) could be synthesized by chloride abstraction from [Cp*Ir(P∧C)Cl] with AgOSO2CF3 and crystallographically characterized. It turned out that this species is the first phosphorus-containing Ir(III) complex which shows a remarkable activity in the cerium ammonium nitrate driven water oxidation reaction. In situ NMR spectroscopic investigations further reveal that water is added selectively to one of the PC double bonds with formation of four stereoisomers. Moreover, [Cp*Ir(P∧C)] species, possibly OH-functionalized but still having Cp* and P∧Cligands contemporary bound to iridium, are present in solution, even under catalytic conditions.
Cyclometalated Phosphinine–Iridium(III) Complexes: Synthesis, Reactivity, and Application as Phosphorus-Containing Water-Oxidation Catalysts
BUCCI, ALBERTO;ZUCCACCIA, Cristiano;MACCHIONI, Alceo
;
2015
Abstract
The novel phosphinine-based coordination compound [Cp*Ir- (P∧C)(CH3CN)]CF3SO3 (P∧C = cyclometalated 2,4,6-triphenylphosphinine) could be synthesized by chloride abstraction from [Cp*Ir(P∧C)Cl] with AgOSO2CF3 and crystallographically characterized. It turned out that this species is the first phosphorus-containing Ir(III) complex which shows a remarkable activity in the cerium ammonium nitrate driven water oxidation reaction. In situ NMR spectroscopic investigations further reveal that water is added selectively to one of the PC double bonds with formation of four stereoisomers. Moreover, [Cp*Ir(P∧C)] species, possibly OH-functionalized but still having Cp* and P∧Cligands contemporary bound to iridium, are present in solution, even under catalytic conditions.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
