Lei Gao - Synthesis, Structures, and Excited-State Geometries of Alkynylgold(I) Complexes

Version 1

      Publication Details (including relevant citation   information):

      European J. Inorg. Chem. 2009(18), 2711-2719


      A series of phosphane- and (N-heterocyclic carbene)gold(I)   complexes were prepared by deprotonation of terminal alkyne   precursors and reaction with the corresponding gold(I) chlorides.   Some ten new compounds are reported; these are characterized by   multinuclear NMR, optical spectroscopy, and elemental analysis.   Crystallographic characterization is reported for five complexes.   Organogold species bearing conjugated aryl substituents on the   alkynyl ligand are luminescent. Density-functional theory   calculations on a model complex suggest that emission and the   first several absorption transitions result from excited states   dominated by the arylacetylide ligand. Excited-state geometry   optimization finds that the lowest-energy triplet state bears   linear, two-coordinate gold(I) with a miniscule lengthening of   the alkynyl carbon–carbon bond. An unusual triplet excited state   having a bent geometry at gold lies at higher energy in   arylacetylide complexes. For the model terminal   acetylideMe3PAuC≡CH, the calculations find this bent   state to be the lowest-energy triplet.(© Wiley-VCH Verlag GmbH   & Co. KGaA, 69451 Weinheim, Germany, 2009)

      Address (URL): http://www3.interscience.wiley.com/journal/122373346/abstract