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Structure and Photochemical Isomerization of the Dinuclear Gold(I) Halide Bis(diphenylphosphanyl)ethylene Complexes: Correlation Between Quantum Yield and Aurophilicity
Author(s) -
Foley Janet B.,
Gay Stanley E.,
Vela Michael J.,
Foxman Bruce M.,
Bruce Alice E.,
Bruce Mitchell R. M.
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700575
Subject(s) - chemistry , isomerization , iodide , intramolecular force , quantum yield , intermolecular force , yield (engineering) , halide , ab initio , ethylene , crystallography , photochemistry , stereochemistry , computational chemistry , molecule , catalysis , inorganic chemistry , organic chemistry , physics , materials science , quantum mechanics , metallurgy , fluorescence
The crystal structures for cis‐ (Ph 2 PCH=CHPPh 2 )(AuI) 2 and trans‐ (Ph 2 PCH=CHPPh 2 )(AuI) 2 are reported. The structure of cis‐ (Ph 2 PCH=CHPPh 2 )(AuI) 2 reveals a short intramolecular Au–Au distance of 2.9526(5) Å, while the structure of trans ‐(Ph 2 PCH=CHPPh 2 )(AuI) 2 shows intermolecular Au–Au distances of 3.2292(7) Å. Structural data for the iodide complexes are compared to previously reported crystal structural data for cis‐ and trans ‐(Ph 2 PCH=CHPPh 2 )(AuCl) 2 and dppbz(AuCl) 2 . The quantum yields for the photochemical isomerization of cis ‐(Ph 2 PCH=CHPPh 2 )(AuX) 2 with 334‐nm light, Φ ( cis → trans ), are 0.204, 0.269, and 0.363 for X = Cl, Br, and I, respectively. Prior results from ab initio calculations on the model cis ‐ and trans ‐Au 2 X 2 C 2 H 2 (PH 2 ) 2 complexes aid in the interpretation of the correlation between the quantum yield for isomerization and the calculated aurophilic attraction potential V ( R e ). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)