Low-Dimensional Architectures in Isomeric -PtCl{PhPCHN(Ar)CHPPh} 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, have been extensively studied using single crystal X-ray crystallography. In the first library, isomeric diphosphines of the type PhPCHN(Ar)CHPPh [-; Ar = CH(Me)(OH)] and, in the second library, amide-functionalised, isomeric ligands PhPCHN{CHC(O)NH(Ar)}CHPPh [-; Ar = CH(Me)(OH)], were synthesised by reaction of PhPCHOH and the appropriate amine in CHOH, and isolated as colourless solids or oils in good yield. The non-methyl, substituted diphosphines PhPCHN{CHC(O)NH(Ar)}CHPPh [, Ar = 3-CH(OH); , Ar = 4-CH(OH)] and PhPCHN(Ar)CHPPh [, Ar = 3-CH(OH)] were also prepared for comparative purposes. Reactions of -, -, or with PtCl(η-cod) afforded the corresponding square-planar complexes -, -, and in good to high isolated yields. All new compounds were characterised using a range of spectroscopic (H, P{H}, FT-IR) and analytical techniques. Single crystal X-ray structures have been determined for , ∙CHOH, ∙CHOH, , , ∙(CH)SO, ∙CHCl, ∙½EtO, ∙½CHCl∙½CHOH, ∙½EtO, , ∙¼HO, ∙EtO, and ∙(CH)SO. The free phenolic group in ∙CHOH, ∙CHOH, ∙(CH)SO, ∙½EtO, ∙¼HO, and ∙(CH)SO exhibits various intra- or intermolecular O-H∙∙∙X (X = O, N, P, Cl) hydrogen contacts leading to different packing arrangements.