AI Article Synopsis
- Two types of organometallic halide complexes, (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X), were created with X being different halogens (I, Br, Cl, F).
- The complexes can undergo two reaction types: breaking the bonds with X or forming a C(aryl)-CF3 bond, and their reactivity varies significantly based on the halogen present.
- Kinetic studies show that the ease of forming bonds depends on the halogen, with a clear trend in bond formation preferences and strength, dictated by the stability of the Au(III)-X bond.
Article Abstract
Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both C(aryl)-X and C(aryl)-CF3 reductive elimination. Mechanistic studies of thermolysis at 122 °C reveal a dramatic reactivity and kinetic selectivity dependence on halide ligand. For X = I or F, zero-order kinetic behavior is observed, while for X = Cl or Br, kinetic studies implicate product catalysis. The selectivity for C(aryl)-CF3 bond formation increases in the order X = I < Br < Cl < F, with exclusively C(aryl)-I bond formation when X = I, and exclusively C(aryl)-CF3 bond formation when X = F. Thermodynamic measurements show that Au(III)-X bond dissociation energies increase in the order X = I < Br < Cl, and that ground state Au(III)-X bond strength ultimately dictates selectivities for C(aryl)-X and C(aryl)-CF3 reductive elimination.
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Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4482415 | PMC |
| http://dx.doi.org/10.1021/jacs.5b04613 | DOI Listing |
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