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 (2-)=1,3-BIS(2-MERCAPTOPHENYLTHIO)-2-PROPANOL(2-))
D. Sellmann et al., 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 (2-)=1,3-BIS(2-MERCAPTOPHENYLTHIO)-2-PROPANOL(2-)), Inorganica Chimica Acta, 237(1-2), 1995, pp. 137-141
Template alkylation of Na-2[Ni('S2C6H4')(2)] With 2,3-dibromo-1-propan
ol 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 symme
trical C-3 bridge carrying the OH function at the central C atom, beca
use the C skeleton of 2,3-dibromo-1-propanol rearranges in the course
of the alkylation reaction. This was proved by independent synthesis o
f 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 de
termination 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 = 1
2.585(4), c = 15.536(4) Angstrom, beta = 93.07(2)degrees, R/R(w) = 0.0
71/0.063.) The Pt centre of 3 . THF exhibits approximately square plan
ar 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.