Structure and Photochemical Isomerization of the Dinuclear Gold(I) Halide Bis(diphenylphosphanyl)ethylene Complexes: Correlation Between Quantum Yield and Aurophilicity
✍ Scribed by Janet B. Foley; Stanley E. Gay; Michael J. Vela; Bruce M. Foxman; Alice E. Bruce; Mitchell R. M. Bruce
- Publisher
- John Wiley and Sons
- Year
- 2007
- Tongue
- English
- Weight
- 155 KB
- Volume
- 2007
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
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)