Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center
نویسندگان
چکیده
منابع مشابه
Uranium-mediated oxidative addition and reductive elimination.
Oxidative addition, and its reverse reaction reductive elimination, constitute two key reactions that underpin organometallic chemistry and catalysis. Although these reactions have been known for decades in main group and transition metal systems, they are exceptionally rare or unknown for the f-block. However, in recent years much progress has been made. In this Perspective article, advances i...
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Herein we report the mechanism of oxidative addition of CF3I to Au(I), and remarkably fast Caryl-CF3 bond reductive elimination from Au(III) cations. CF3I undergoes a fast, formal oxidative addition to R3PAuR' (R = Cy, R' = 3,5-F2-C6H4, 4-F-C6H4, C6H5, 4-Me-C6H4, 4-MeO-C6H4, Me; R = Ph, R' = 4-F-C6H4, 4-Me-C6H4). When R' = aryl, complexes of the type R3PAu(aryl)(CF3)I can be isolated and charac...
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Ab initio calculations (Hartree-Fock, generalized valence bond, and configuration interaction), utilizing relativistic core potentials, have been used to follow the oxidative addition of Hz to Pt(PH,),. We find an activation barrier of 2.3 kcal/mol and an exothermicity of 15.9 kcal/mol. From examination of the geometries and wave functions, we find that up to the transition state the H-H bond i...
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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...
متن کاملExceptionally Fast Carbon-Carbon Bond Reductive Elimination from Gold(III)
Reductive elimination of carbon-carbon bonds occurs in numerous metal-catalysed reactions. This process is well documented for a variety of transition metal complexes. However, carbon-carbon bond reductive elimination from a limited number of Au(III) complexes has been shown to be a slow and prohibitive process that generally requires elevated temperatures. Herein we show that oxidation of a se...
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ژورنال
عنوان ژورنال: Journal of the American Chemical Society
سال: 2018
ISSN: 0002-7863,1520-5126
DOI: 10.1021/jacs.8b01411