Synthesis and derivatization, structures and transition metal chemistry of a new large bite bis(phosphinite) derived from bis(2-hydroxy-1-naphthyl)methane

Bis(2-hydroxy-1-naphthyl)methane reacts with chlorodiphenylphosphine to afford the bis(phosphinite), Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2 (1) in good yield. The bis(phosphinite) 1 reacts with elemental sulfur or selenium to give the corresponding disulfide or diselenide; the structure of the selenium derivative, Ph2P(Se){(–OC10H6)(μ-CH2)(C10H6O–)}P(Se)Ph2 (3) is confirmed by X-ray crystal structure analysis. Treatment of the ligand 1 with platinum metal derivatives results in the formation of ten-membered chelate complexes with the ligand showing an η2-mode of coordination. The elucidation of the structures of the products is based on NMR (1H and 31P) spectroscopic data. Molecular structures of [CpRuCl{η2-Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2-κP,κP}] (4) and [PtCl2{η2-Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2-κP,κP}] (7) are determined by single crystal X-ray studies.