Preparation and properties of rhodium(I) and iridium(I) diolefin complexes of heterodifunctional phosphorus–imine chelating ligands and a related iminophosphine. ¹⁰³Rh NMR parameters of the rhodium complexes obtained via indirect two-dimensional ³¹P, ¹⁰³Rh{¹H} NMR spectroscopy

Treatment of [M(cod)Cl] 2 (M = Rh, Ir) with iminophosphoranophosphine ligands of the type Ph 2 PQP(Ph 2 )=NSiMe 3 (Q = CH 2 , CH 2 CH 2 , 1,2-C 6 H 4 ) afforded the new metallacycles [Formula: see text] through elimination of Me 3 SiCl, ultimately "anchoring" the ligand to the metal through a metal–nitrogen σ bond. The phosphine functionality completes the chelate. Cationic complexes of the type [M(cod)L 2 ] + PF 6 − (M = Rh or Ir; L 2 = Ph 2 PQPPh 2 NR where Q = CH 2 , CH(CH 3 ), 1,2-C 6 H 4 , and R = p-C 6 F 4 CN, C 6 H 2 F(NO 2 ) 2 , and C 6 H 3 (NO 2 ) 2 or L = Ph 2 PN=C(H)Ph) were readily prepared by treating [M(cod)Cl] 2 with L 2 and KPF 6 . The detection and chemical shift determination of the insensitive 103 Rh nucleus was easily accomplished via 31 P detected indirect two-dimensional 31 P, 103 Rh{ 1 H} NMR spectroscopy. The 103 Rh, 1 H, and 31 P NMR data are discussed.