Copper complexes of the functionalised tripodal ligand tris(2-pyridyl)methylamine and its derivatives †

Abstract
The coordination chemistry of the new tripodal ligand tris(2-pyridyl)methylamine (tpm) with copper(I), copper(II) and zinc(II) has been investigated. The synthesis of tpm can readily be modified to access a variety of related tripodal ligands such as 2-(methylsulfanyl)-1,1-di(2-pyridyl)ethylamine (mde); in addition, the primary amine function can be derivatised to extend further the range of complexes obtained. tpm itself is a versatile ligand, showing three distinct coordination modes: bidentate (py, NH2), tridentate (2py, NH2) and tridentate (3py). Complexes of stoichiometries Cu(tpm)n (n = 1–3) have been obtained. The (2py, NH2) coordination mode is illustrated by the crystal structure of [Cu(tpm)2][BF4]2·Me2CO, whilst (3py) coordination is found in the crystal structures of [Cu(SO4)(tpm)(H2O)]·3H2O, [{Cu(tpm)}2Br3]Br·3MeOH and also the zinc complex [Zn(tpm)(H2O)3]2[Zn(H2O)6][SO4]3·3H2O. Amide derivatives of tpm give complexes of stoichiometry CuL2, and the crystal structures of [Cu(tpma)2][BF4]2 [tpma = tris(2-pyridyl)methylacetamide] and [Cu(tpms)2]·8H2O {tpmsH = 4-oxo-4-[tris(2-pyridyl)methylamino]butanoic acid} have been determined. The crystal structure of the sulfate-bridged dimeric complex [{Cu(SO4)(mde)}2]·3H2O shows the mde ligand to be tridentate, with (2py, NH2) coordination.

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