Synthesis, electronic structure and interaction of rhodium(I) and iridium(I) bisimine-acenaphthalene complexes with CO2

The bis(arylimino)acenaphthalene (BIAN) group of α-diimine compounds has shown promising electron sink behaviour and redox non-innocent activity as ligands to main transition metals. Here we present a series rhodium(I) iridium(I) complexes BIAN derivatives with 2,6-diisopropylphenyl (DippBIAN, DB) 2,4,6-trimethylphenyl (MesBIAN, MB), featuring various withdrawing donating ancillary ligands. crystal structures square planar 1b [RhMB(cod)]PF6, 1d [IrMB(cod)]PF6, 2a [RhDB(CO)2]PF6, 2b [RhMB(CO)2]PF6, 2c [IrDB(CO)2]PF6 3a [RhDB(CO)(PEt3)]PF6 are reported, well the pyramidal structure 4c [IrDB(cod)Cl]. C-N C-C bond lengths within bisimine moiety for suggest that DippBIAN in reduced state, however, all other data from our multi-technique analyses correspond results neutral These contrasting indicative DippBIAN’s behaviour, accepting additional density metal centre due push–pull mechanism between electrochemical study non-coordinating solvent CH2Cl2 revealed featured at least one reversible, ligand-centred reduction event less negative potentials (above –1.0 V vs Ag/Ag+). In addition, preliminary electrocatalytic CO2 interaction complex 3a, paving way exploring heterogeneous catalysis on these class