Synthesis, crystal structures and dynamic NMR studies of novel trinuclear copper(I) halide complexes with 2,5-bis[(diphenylphosphino)methyl]thiophene
Abstract
Novel trinuclear copper(I) halide complexes with 2,5-bis[(diphenylphosphino)methyl]thiophene (dpmt), [Cu3(µ3-X)(µ-X)2(µ-dpmt)2] (X = I 1, Br 2 or Cl 3), have been synthesized and structurally characterised. They have unusual three-runged ladder structures with one triple-bridging and two double-bridging halide atoms. Two of the CuI are tetrahedrally co-ordinated and one, in the middle of the structure unit, has trigonal co-ordination geometry. The trinuclear Cu3(µ3-X)(µ-X)2 framework shows some changes with halide anion X due to the size effect and intramolecular non-bonding Cu· · ·
Cu and X
· · ·
X interactions. The NMR studies showed that the trinuclear framework is retained in solution for 1 (X = I), is in equilibrium with Cu3(µ-X)3 for 2 (X = Br) and changes to Cu3(µ-Cl)3 for 3 (X = Cl), an effect attributable to the decrease of halide size from iodide to chloride. The frameworks in the solutions of 2 and 3 exhibit fluxional behaviour involving bromine and chlorine mobility respectively.