Transition metal complexes with sulfur ligands CXI. Skeletal rearrangement of 2,3-dibromo-1-propanol in the template alkylation of [Ni(‘S2C6H4’)]2− (. Syntheses of [M(‘S4-C3OH’)] complexes (M=NiII,PtII; )
1995; Elsevier BV; Volume: 237; Issue: 1-2 Linguagem: Inglês
10.1016/0020-1693(95)04673-w
ISSN1873-3255
AutoresDieter Sellmann, Petra Bail, Falk Knoch, Matthias Moll,
Tópico(s)Nanocluster Synthesis and Applications
ResumoTemplate alkylation of Na2[Ni(‘S2C6H4’)2] with 2,3-dibromo-1-propanol yielded [Ni(‘S4-C3OH’)] (1) from which the free thiol ‘S4-C3OH’-H2 (2) was obtained by hydrolysis with aqueus HCl. 2 contains a symmetrical C3 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 Na2[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(‘S4-C3OH’)]·THF (3·THF) which is homologous to 1. (Crystal data of 3·THF: monoclinic, P21c, a=10.173(3), b=12.585(4), c=15.536(4) Å, β=93.07(2)°, R/Rw=0.071/.0063.) The Pt centre of 3·THF exhibits approximately square planar coordination with nearly equidistant bond lengths to the thioether and thiolate sulfur donors. The rearrangement of the C skeleton of 2,3-dibromo-1-propanol is traced back to the neighbouring-group effect of the OH function.
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