title: Synthesis, characterisation and reactivity of copper(I) amide complexes and studies on their role in the modified Ullmann amination reaction.
abstract: A series of copper(I) alkylamide complexes have been synthesised; copper(I) dicyclohexylamide (1), copper(I) 2,2,6,6-tetramethylpiperidide (2), copper(I) pyrrolidide (3), copper(I) piperidide (4), and copper(I) benzylamide (5). Their solid-state structures and structures in [D6 ]benzene solution are characterised, with the aggregation state in solution determined by a combination of DOSY NMR spectroscopy and DFT calculations. Complexes 1, 2 and 4 are shown to exist as tetramers in the solid state by X-ray crystallography. In [D6 ]benzene solution, complexes 1, 2 and 5 were found by using (1) H DOSY NMR to exist in rapid equilibrium between aggregates with average aggregation numbers of 2.5, 2.4 and 3.3, respectively, at 0.05 M concentration. Conversely, distinct trimeric, tetrameric and pentameric forms of 3 and 4 were distinguishable by one-dimensional (1) H and (1) H DOSY NMR spectroscopy. Complexes 3-5 are found to react stoichiometrically with iodobenzene, in the presence or absence of 1,10-phenanthroline as an ancillary ligand, to give arylamine products indicative of their role as potential intermediates in the modified Ullmann reaction. The role of phenanthroline has also been explored both in the stoichiometric reaction and in the catalytic Ullmann protocol.
authors: Department of Chemistry, Imperial College London, South Kensington, London, SW7 2AZ (UK).
authors: Simon
authors: S
authors: Sung
authors: D Christopher
authors: DC
authors: Braddock
authors: Alan
authors: A
authors: Armstrong
authors: Colin
authors: C
authors: Brennan
authors: David
authors: D
authors: Sale
authors: Andrew J P
authors: AJ
authors: White
authors: Robert P
authors: RP
authors: Davies
keywords: Ullmann reaction; amination; copper; homogeneous catalysis; structure elucidation