Synthesis and Structural Aspects of Rigid Aryl-palladium(II) and-Platinum(II) Complexes. X-ray Crystal Structure of o,o'-Bis(dimethylamino)methyl>phenylplatinum(II) Bromide

Article abstract of DOI:10.1016/0022-328X(86)80460-0

The tridentate monoanionic ligand o,o'-(Me2NCH2)2C6H3 (NCN') has been used to synthesize novel aryl-palladium(II) and -platinum(II) complexes and (M= Pt, Pd).Three synthetic procedures are described, namely: (i) reaction of the cationic complex ⁺ with KX or NaX to give (X= Cl, I, O2CH, NCS, NO2, NO3); (ii) displacement reactions using AgX with to give (X= CN, O3SCF3, O2CMe, O2CCF3) and (iii) transmetallation reactions of with organolithium to give (R= Ph, o-, m-, p-tolyl, C<*>CPh, C<*>C-p-tolyl).All the complexes have been characterized by elemental analysis IR, 1H NMR and 13C NMR spectroscopy.An X-ray diffraction study has shown that (2) has a square-planar structure, in which the tridentate ligand is bonded via C(ipso) (Pt-C 1.90(1) Angstroem, and two mutually trans-N donor atoms (Pt-N(1) 2.07(1), Pt-N(2) 2.09(1) Angstroem.The fourth site trans to C(ipso) is occupied by bromine (Pt-Br 2.526(2) Angstroem).The two chelate rings (N-Pt-C(ipso) 82.9(5) and 81.5(5) grade) are distinctly puckered, with the two NMe2 groups on opposite sides of the aryl plane.The Pt-C bond in 2 is shorter than analogous bonds in other arylplatinum(II) complexes, as a result of (i) the rigid structure of the tridentate ligand and (ii) the presence of two hard N donor atoms trans to one another across the platinum centre.