S-, O-, O, O′- p-toluenesulfinato complexes of iron(II), cobalt(II) and nickel(II) with polydentate tripod-like phosphines, crystal structure of 1,1,1-tris(diphenylphosphinomethyl)ethane p-toluenesulfinatocobalt(II) perchlorate

Abstract

Reaction of sodium p-toluenesulfinate with iron(II), cobalt(II) and nickel(II) aquo ions in the presence of the poly(tertiary phosphines) 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos), tris(2-diphenylphosphinoethyl)amine (np 3) and tris(2-diphenylphosphinoethyl)phosphine (pp 3) gives five-coordinated p-toluenesulfinato complexes of formulae [(triphos)Co( p-tolSO 2)]ClO 4 and [LM( p-tolSO 2)]BPh 4 (L = pp 3, M = Fe, Co, Ni; L = np 3, M = Co, Ni). The nickel derivatives are diamagnetic with the p-toluenesulfinate ligand bonded to the metal through the sulfur atom. The iron and cobalt complexes are paramagnetic, low or high spin, with the p-toluenesulfinate ion linked to the metal via one oxygen (np 3 and pp 3 derivatives) or both oxygen atoms (cobalt-triphosderivative). The structure of [(triphos)Co( p-tolSO 2)]ClO 4 has been determined from three-dimensional X-ray data collected by counter methods. The crystals are monoclinic, space group P2 1/ n with a = 20.942(9), b =, 9.652(4), c= 22.040(8), Å, β, = 96.86(5)°, d c = 1.407 gcm −3 for Z = 4. Full-matrix least-squares refinements converged at the conventional R factor of 0.063 for 5573 observed reflections. The complex cation has a distorted square pyramidal geometry with the sulfinate group acting as a bidentate ligand through the two oxygen atoms.