Transition metal chemistry of large-bite bisphosphines, N,N-bis(diphenylphosphinobenzyl)-N-phenylamine and bis(2-diphenylphosphinobenzyl)ether

• Large bite bisphosphines containing N and O atoms in the ligand framework have been synthesized.
• Cis and trans complexes of Pd(II) and Pt(II) have been isolated.
• Chelating as well as bridging coordination modes have been observed.

Oxidation reactions and transition metal chemistry of large bite bisphosphines N,N-bis(diphenylphosphinobenzyl)-N-phenylamine (1) and bis(2-diphenylphosphinobenzyl)ether (2) are described. The reactions of 1 and 2 with chalcogenides in 1:2 M ratios afforded bis-chalcogenides. Reactions of 1 and 2 with M(COD)Cl2 (M = Pd, Pt) in 1:1 M ratios yielded trans-[MCl2{C6H5N(CH2-2-C6H4PPh2)2}-κ2P,P] (M = Pd, 9; Pt, 10) and cis-[MCl2{O(CH2-2-C6H4PPh2)2}-κ2P,P] (M = Pd, 11; Pt, 12), respectively. Treatment of 1 and 2 with [Pd(η3-C3H5)Cl]2 and [RuCl2(η6-p-cymene)]2 in 1:1 M ratios produced dinuclear complexes of the type [Pd2Cl2(η3-C3H5)2-μ-{C6H5N(CH2-2-C6H4PPh2)2}-μP,P] (13), [Pd2Cl2(η3-C3H5)2-μ-{O(CH2-2-C6H4PPh2)2}-μP,P] (14), [{Ru(η6-p-cymene)}2-μ-{C6H5N(CH2-2-C6H4PPh2)2}-μP,P] (17) and [{Ru(η6-p-cymene)}2-μ-{O(CH2-2-C6H4PPh2)2}-μP,P] (18). The reactions of 1 and 2 with one half equivalent of [Pd(η3-C3H5)Cl]2 followed by the addition of AgOTf yielded chelate complexes [Pd(η3-C3H5){C6H5N(CH2-2-C6H4PPh2)2}-κ2P,P]OTf (15) and [Pd(η3-C3H5){O(CH2-2-C6H4PPh2)2}-κ2P,P]OTf (16). The reactions of 1 and 2 with [AuCl(SMe2)] in 1:2 and 1:1 M ratios afforded dinuclear [(Au2Cl2)C6H5N(CH2-2-C6H4PPh2)2-μ-P,P] (19), [Au2Cl2O(CH2-2-C6H4PPh2)2-μ-P,P] (20) and mononuclear complexes [(AuCl)C6H5N(CH2-2-C6H4PPh2)2-κ2P,P] (21), [(AuCl)O(CH2-2-C6H4PPh2)2-κ2P,P] (22), with the ligands exhibiting bridging and chelating modes of coordination. The crystal structures of 3, 7, 8, 11, 12, 15 and 19 have been established by X-ray diffraction studies.

This paper describes the transition metal chemistry of N and O bridged large bite bisphosphines N,N-bis(diphenylphosphinobenzyl)-N-phenylamine and bis(2-diphenylphosphinobenzyl)ether.Figure optionsDownload as PowerPoint slide