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

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)Cl-2 (M = Pd, Pt) in 1:1 M ratios yielded trans-[MCl2{C6H5N(CH2-2-C6H4PPh2)(2)}-kappa P-2,P] (M = Pd, 9; Pt, 10) and cis-[MCl2{O(CH2-2-C6H4PPh2)(2)}-kappa P-2,P] (M = Pd, 11; Pt, 12), respectively. Treatment of 1 and 2 with [Pd(eta(3)-C3H5)Cl](2) and [RuCl2(eta(6)-p-cymene)](2) in 1:1 M ratios produced dinuclear complexes of the type [Pd2Cl2(eta(3)-C3H5)(2)-mu-{C6H5N(CH2-2-C6H4PPh2)(2)}-mu P,P] (13), [Pd2Cl2(eta(3)-C3H5)(2)-mu-{O(CH2-2-C6H4PPh2)(2)}-mu P,P] (14), [{Ru(eta(6)-p-cymene)}(2)-mu-{C6H5N(CH2-2-C6H4PPh2)(2)}-mu P,P] (17) and [{Ru(eta(6)-p-cymene)}(2)-mu-{O(CH2-2-C6H4PPh2)(2)}-eta P,P] (18). The reactions of 1 and 2 with one half equivalent of [Pd(eta(3)-C3H5)Cl](2) followed by the addition of AgOTf yielded chelate complexes [Pd(eta(3)-C3H5){C6H5N(CH2-2-C6H4PPh2)(2)}-kappa P-2,P]OTf (15) and [Pd(eta(3)-C3H5){O(CH2-2-C6H4PPh2)(2)}-kappa P-2,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)-mu-P,P] (19), [Au2Cl2O(CH2-2-C6H4PPh2)(2)-mu-P,P] (20) and mononuclear complexes [(AuCl)C6H5N(CH2-2-C6H4PPh2)(2)-kappa P-2,P] (21), [(AuCl)O(CH2-2-C6H4PPh2)(2)-kappa P-2,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. (C) 2016 Elsevier B.V. All rights reserved