Triangular tricopper(i) clusters supported by donor-substituted triazacyclohexanesElectronic supplementary information (ESI) available: Plots for structures not shown in the article, DFT results including a typical input file, additional orbital contour plots and xyz files for optimised structures and calculated 1H and 13C NMR shifts. CCDC reference numbers 707388–707395. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/b819268e

Autor: Randolf D. Köhn, Lorena Tomás Laudo, Zhida Pan, Fredy Speiser, Gabriele Kociok-Köhn
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Zdroj: Dalton Transactions: An International Journal of Inorganic Chemistry; Jun2009, Vol. 2009 Issue 23, p4556-4568, 13p
Abstrakt: Triazacyclohexanes (R3TAC, 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 [R3TAC(CuX)3] (R = 2-pyridylmethyl (2a, 3a), 5-tbutyl-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, 3hand 4ishow triangular halide-bridged Cu3clusters 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. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index