6533b861fe1ef96bd12c4c89

RESEARCH PRODUCT

Synthesis of new orthometallated iridium(III) compounds by chemical and electrochemical methods

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Abstract Replacement of one phosphine ligand in IrCl 3 (η 2 -PCBr)(η 1 -PCBr) ( 1 ) (PCBr = P( o -BrC 6 F 4 )Ph 2 ), by various P-donor ligands has given compounds of stoichiometry IrCl 3 (η 2 -PCBr)L ( 3 : L = PMePh 2 ; 4 : L = P( p -MeC 6 H 4 ) 3 ; 5 : L = P(OMe) 3 , 6 : L = P(OPh) 3 ). All of these show two irreversible reduction peaks in the range −1.1, −1.3 and ca. −2.0 V. The electrochemical reduction of compound 1 at −1.5 V (at 0°C) leads to a very reactive iridium(I) species, probably IrCl(PCBr) 2 , which undergoes intramolecular orthometallation at room temperature. Three compounds are obtained as the results of this chemical conversion: IrBr 2 (PC)(PCBr) ( 7 ), IrCl 2 (PC)(PCBr) ( 8 ) and (as a mixture of isomers) IrClBr(PC)(PCBr) ( 9 ) (PC = P(C 6 F 4 )Ph 2 ). The different behaviour of rhodium and iridium complexes in these reactions are discussed.