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

Abstract

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.