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Synthesis of an Iridium Peroxido Complex and Its Reactivity Towards Brønsted Acids

2015; Wiley; Volume: 2015; Issue: 19 Linguagem: Inglês

10.1002/ejic.201500384

1099-0682

Hanna Baumgarth, Thomas Braun, Beatrice Braun, Reik Laubenstein, Roy Herrmann,

CO2 Reduction Techniques and Catalysts

Abstract Treatment of the iridium(I) complex trans ‐[Ir(4‐C 5 F 4 N)(CN t Bu)(P i Pr 3 ) 2 ] ( 2 ) with O 2 or H 2 O 2 gave the iridium(III) peroxido complex trans ‐[Ir(4‐C 5 F 4 N)(O 2 )(CN t Bu)(P i Pr 3 ) 2 ] ( 3a ). The peroxido complex 3a reacts with Brønsted acids to give the iridium(III) complexes cis ‐[Ir(4‐C 5 F 4 N)(X) 2 (CN t Bu)(L)(P i Pr 3 )] ( 4 : X = Cl, L = P i Pr 3 , 5 : X = CF 3 COO, L = H 2 O) and hydrogen peroxide. In the presence of formic acid, 3a yields the carbonato complex trans ‐[Ir{κ 2 ‐ O C(O) O }(4‐C 5 F 4 N)(CN t Bu)(P i Pr 3 ) 2 ] ( 6 ) as the main product. Reactions between formic acid or dihydrogen and the iridium(I) complex 2 give the isomeric dihydrido complexes trans , trans ‐[Ir(4‐C 5 F 4 N)(H) 2 (CN t Bu)(P i Pr 3 ) 2 ] ( 7a ) and cis , trans ‐[Ir(4‐C 5 F 4 N)(H) 2 (CN t Bu)(P i Pr 3 ) 2 ] ( 9a ), respectively.