title: Triangular tricopper(I) clusters supported by donor-substituted triazacyclohexanes.
abstract: Triazacyclohexanes (R(3)TAC,1a-i ) with pyridyl or thioether functionalities (R) in the N-substituents react with three equivalents of CuX (X = Cl (2), Br (3) or I (4)) in MeCN to give the triangular tri-copper clusters [R(3)TAC(CuX)(3)] (R = 2-pyridylmethyl (2a, 3a ), 5-(t)butyl-2-pyridyl (3b). 2-(3-phenylpropylthio)ethyl (3c), 2-(2-ethyl-butylthio)ethyl (3d), 2-(4-heptylthio)ethyl (2e, 3e ), 2-(1-heptylthio)ethyl (3f), 2-(2,4,6-trimethyl-benzylthio)ethyl (3g), 2-(o-methyl-benzylthio)ethyl (3h) and 2-(o-fluoro-benzylthio)ethyl (2i, 3i 4i)). The thioether complexes are stable towards air and water. The bromide bridge in the clusters can be replaced by chloride (2c, e, f, i) or iodide (4c, e, f, i ) by the reaction of a dichloromethane solution of the cluster with aqueous NaI or AgCl, respectively. Crystal structures of 2a, 3a, 3b, 2e, 3h and show triangular halide-bridged Cu(3) clusters capped by the triazacyclohexane and stabilised by the coordination of one pyridyl or thioether arm to each copper atom. DFT calculations confirm the NMR assignments and reveal the electronic structure of the copper triangle.
authors.affiliation: Department of Chemistry, University of Bath, Bath, UKBA2 7AY. r.d.kohn@bath.ac.uk
authors.forename: Randolf D
authors.initials: RD
authors.lastname: Köhn
authors.forename: Lorena
authors.initials: L
authors.lastname: Tomás Laudo
authors.forename: Zhida
authors.initials: Z
authors.lastname: Pan
authors.forename: Fredy
authors.initials: F
authors.lastname: Speiser
authors.forename: Gabriele
authors.initials: G
authors.lastname: Kociok-Köhn
mesh_terms: D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003510:Cyclohexanes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry; D011789:Quantum Theory; D012995:Solubility; D021241:Spectrometry, Mass, Electrospray Ionization; D013440:Sulfides / Q000737:chemistry
chemical_list: D003510:Cyclohexanes; D009942:Organometallic Compounds; D011725:Pyridines; D013440:Sulfides; D003300:Copper