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DOI: 10.1039/A806380J (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1998, 3737-3746

Ligands containing alternating 2,6-linked pyridine and 2,5-linked thiophene units[hair space]1

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Otto Meth-Cohn and Hui Jiang

Abstract

A variety of linear assemblies of alternating pyridine (2,6-linked) [P] and thiophene (2,5-linked) [T] units have been generated with up to seven units and their macrocyclisation investigated. The optimal methods involved the palladium(>0>) catalysed reaction of thienyl Grignard reagents with bromopyridines. In this way were made TPT, TPTPT, TPTPTPT, BrPTPBr and various XCH2PTPTPCH2X derivatives (X = H, Br, OH, OR and SBu-t). Alternative routes whereby pyridine units were 2,6-linked by CH2SCH2 units, with the intention of converting the bridge groups into thiophenes by a Hinsberg reaction, were also studied. The latter products {(HOCH2[P]CH2)2S and (HOCH2[P]CH2SCH2)2[P][hair space]} proved to be highly effective ligands for transition metals, especially divalent ones such as Co2+, Ni2+ and Zn2+. No macrocyclisations were effective.

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