Low-Dimensional Architectures in Isomeric cis-PtCl(2){Ph(2)PCH(2)N(Ar)CH(2)PPh(2)} Complexes Using Regioselective-N(Aryl)-Group Manipulation

The solid-state behaviour of two series of isomeric, phenol-substituted, aminomethylphosphines, as the free ligands and bound to Pt(II), have been extensively studied using single crystal X-ray crystallography. In the first library, isomeric diphosphines of the type Ph(2)PCH(2)N(Ar)CH(2)PPh(2) [1a–e; Ar = C(6)H(3)(Me)(OH)] and, in the second library, amide-functionalised, isomeric ligands Ph(2)PCH(2)N{CH(2)C(O)NH(Ar)}CH(2)PPh(2) [2a–e; Ar = C(6)H(3)(Me)(OH)], were synthesised by reaction of Ph(2)PCH(2)OH and the appropriate amine in CH(3)OH, and isolated as colourless solids or oils in good yield. The non-methyl, substituted diphosphines Ph(2)PCH(2)N{CH(2)C(O)NH(Ar)}CH(2)PPh(2) [2f, Ar = 3-C(6)H(4)(OH); 2g, Ar = 4-C(6)H(4)(OH)] and Ph(2)PCH(2)N(Ar)CH(2)PPh(2) [3, Ar = 3-C(6)H(4)(OH)] were also prepared for comparative purposes. Reactions of 1a–e, 2a–g, or 3 with PtCl(2)(η(4)-cod) afforded the corresponding square-planar complexes 4a–e, 5a–g, and 6 in good to high isolated yields. All new compounds were characterised using a range of spectroscopic ((1)H, (31)P{(1)H}, FT–IR) and analytical techniques. Single crystal X-ray structures have been determined for 1a, 1b∙CH(3)OH, 2f∙CH(3)OH, 2g, 3, 4b∙(CH(3))(2)SO, 4c∙CHCl(3), 4d∙½Et(2)O, 4e∙½CHCl(3)∙½CH(3)OH, 5a∙½Et(2)O, 5b, 5c∙¼H(2)O, 5d∙Et(2)O, and 6∙(CH(3))(2)SO. The free phenolic group in 1b∙CH(3)OH, 2f∙CH(3)OH(,) 2g, 4b∙(CH(3))(2)SO, 5a∙½Et(2)O, 5c∙¼H(2)O, and 6∙(CH(3))(2)SO exhibits various intra- or intermolecular O–H∙∙∙X (X = O, N, P, Cl) hydrogen contacts leading to different packing arrangements.