Di- and Triazaphospholes as Ligands for Ruthenium(II) and Iridium(III) Complexes

The reaction of the azaphospholes 5-methyl-2-phenyl-1,2,3-diazaphospole (PDAP) and 2-methyl-2-phenyl-1,2,4,3-triazaphospole (PTAP) with the dimers [LMCl2](2) (LM = eta(6)-C6Me6Ru, eta(5)-C5Me5Ir) of ruthenium(II) and iridium(III) only occurs in presence of nucleophiles such as EtOH or H2O leading to their metal-coordination after cleavage of the dimers. [(eta(6)-C6Me6)RuCl2](2) reacts with PDAP and EtOH in the molar ratio 0.5:1:1 to give the phosphorus-coordinated complex (eta(6)-C6Me6)RuCl2(P-PDAP-EtOH) (1). In the case of [(eta(5)-C5Me5)IrCl2](2), the triazaphosphole PTAP was used in the presence of EtOH or H2O yielding the analogous products (eta(5)-C5Me5)IrCl2(P-PTAP center dot EtOH) (2) or (eta(5)-C5Me5)IrCl2(P-PTAP center dot H2O) (3). In 1-3, the former aromatic azaphosphole (sigma(2), lambda(3)-P) has been converted by 1,2 addition of EtOH or H2O to their P=C or P=N double bond with the nucleophiles EtO- and OH- bonded to phosphorus (sigma(2), lambda(3)-P). Complexes 1-3 with a piano-stool configuration were characterized by elemental analysis, P-31 NMR spectroscopy and single-crystal X-ray diffraction.