Complexes of sterically-hindered diaminophosphinothiolate ligands with Rh(I), Ni(II) and Pd(II)

Two new sterically demanding diaminophosphinothiolate ligands (HL1 and HL2) have been prepared and the X-ray crystal structure of the Li salt of HL2 has been determined. The complex [Pd(L1)2] was fully characterized, but in contrast to other phosphinothiolates, complexes with the M(L)3 stoichiometry could not be prepared. Reaction of LH1 with Ni(II) led to cleavage of the arythiolate group and isolation of a thiolate bridged dimer, confirmed by an X-ray crystal structure. The Rh(I) complexes [Rh(nbd)L] (L = L1, L2) were characterized including an X-ray structure.

Graphical abstractTwo sterically demanding PS-ligands have been prepared and reacted with several transition metal precursor complexes. It appeared that increased steric hindrance at the phosphorus prevents formation of octahedral M(PS)3 type complexes but square planar complexes of the type M(PS)2 and LM(PS) were isolated and characterized in the solid and solution states.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► New bulky bidentate PS-ligand synthesis. ► Four-coordinate square planar complexes. ► Rhodium(I), Palladium(II) and Nickel(II).