The synthesis and crystal structures of the first examples of six-membered inorganic iridacycles containing the [(Ph2PE)(2)N](-) ligand (E = S or Se)

The reaction of the potassium salt of either imidotetraphenyldithiodiphosphinate (L-1) or imidotetraphenyldiselenodiphosphinate (L-2) with [Cp*IrCl(mu-Cl)](2) in THF yields the complexes Cp*Ir{Ph2P(S)NP(S)Ph-2-S,S'}Cl (1) and Cp*Ir{Ph2P(Se)NP(Se)Ph-2-Se,Se'}Cl (2), respectively. Compounds 1 and 2 can be further converted into a range of new mononuclear species comprising mixed [Cp*,E-3] donor sets by metathetic exchange of the chloro ligand for either thiocyanate or selenocyanate. These are the first examples of neutral monomeric Ir(III) complexes which have this ligand set. All compounds were characterised by a combination of NMR spectroscopy (H-1 and P-31{H-1}), IR spectroscopy, microanalysis and X-ray crystallography. (C) 1999 Elsevier Science S.A. All rights reserved.