Syntheses and Molecular Structure of Some Rh and Ru Complexes with the Chelating Diphenyl (2-Pyridyl)phosphine Ligand

The rhodium(III) complex mer,cis-[RhCl3(PPh2py-P,N)(PPh2py-P)] (1) (PPh2py = diphenyl (2-pyridyl)phosphine) has
been prepared from RhCl3·3H2O and PPh2py and converted to the trans,cis-[RhCl2(PPh2py-P,N)2]PF6 (2) in acetone
solution by treatment with Ag+ and PF6-. Ruthenium(III) and ruthenium(II) compounds with PPh2py, mer,cis-[RuCl3(PPh2py-P,N)(PPh2py-P)] (3) and mer-[RuCl(PPh2py-P,N)2(PPh2py-P)]Cl (5) have been obtained from DMSO
precursor complexes. In a chloroform solution, complex (5) isomerizes to fac-[RuCl(PPh2py-P,N)2(PPh2py-P)]Cl
(fac-5). All compounds have been characterized by MS, UV−vis, IR, and 1H and 31P{1H} NMR spectroscopy, and
the Ru(III) compound has been characterized by EPR spectroscopy as well. The crystal structures of 1, 2, 3, and
fac-5 have been determined. In all compounds under investigation, at least one pyridylphosphine acts as a chelate
ligand. The 31P chemical shifts for chelating PPh2py-P,N depend on the Ru−P bond lengths.