Reaction of azaphospholes (L ) [2-phosphaindolizines (1) and I ,3-azaphospholo[S, I-a]isoquinolines (2)] with [η⁵_-(Cp*RhC₂L₂ (Cp* = pentamethylcycloPentadienyl) and [Ru( η⁶-cymene)CI₂ in 2: I molar ratio in dichloromethane yields mononuclear complexes of the type [Cp*RhCl₂ L)].H₂0 and [Ru(cymene)Cl_2⁽ L)].H₂0. These complexes have been characterized by elemental analysis, FAB mass, IR and NMR (¹H and ³¹p) spectral data. Stereochemistry of these complexes has been discussed based on NMR data. NMR studies reveal adynamic equilibrium between covalent and ionic forms of the complexes derived from 1 in solution.