TRANSITION-METAL COMPLEXES WITH SULFUR LIGANDS .111. SKELETAL REARRANGEMENT OF 2,3-DIBROMO-1-PROPANOL IN THE TEMPLATE ALKYLATION OF [NI(S2C6H4)](2-) (S2C6H4(2-)=1,2-BENZENEDITHIOLATE(2-)) - SYNTHESES OF [M(S-4-C3OH)] COMPLEXES (M=NI-II, PT-II S-4-C3OH(2-)=1,3-BIS(2-MERCAPTOPHENYLTHIO)-2-PROPANOL(2-))

Template alkylation of Na-2[Ni('S2C6H4')(2)] With 2,3-dibromo-1-propanol yielded [Ni('S-4-C3OH')] (1) from which the free thiol 'S-4-C3OH'-H-2 (2) was obtained by hydrolysis with aqueous HCl. 2 contains a symmetrical C-3 bridge carrying the OH function at the central C atom, because the C skeleton of 2,3-dibromo-1-propanol rearranges in the course of the alkylation reaction. This was proved by independent synthesis of 2 from Na-2[Ni('S2C6H4')(2)] and 1,3-dibromo-2-propanol followed by hydrolysis of the resulting nickel complex, and the X-ray structure determination of [Pt('S-4-C3OH')]. THF (3 . THF) which is homologous to 1. (Crystal data of 3 . THF: monoclinic, P2(1)/c, a = 10.173(3), b = 12.585(4), c = 15.536(4) Angstrom, beta = 93.07(2)degrees, R/R(w) = 0.071/0.063.) The Pt centre of 3 . THF exhibits approximately square planar coordination with nearly equidistant bond lengths to the thioether and thiolate sulfur honors. The rearrangement of the C skeleton of 2,3-dibromo-1-propanol is traced back to the neighbouring-group effect of the OH function.