The synthesis and characterization of hitherto hypothetical AuIIIπ-alkyne complexes is reported. Bonding and stability depend strongly on the trans effect and steric factors. Bonding characteristics shed light on the reasons for the very different stabilities between the classical alkyne complexes of PtIIand their drastically more reactive AuIIIcongeners. Lack of back-bonding facilitates alkyne slippage, which is energetically less costly for gold than for platinum and explains the propensity of gold to facilitate C−C bond formation. Cycloaddition followed by aryl migration and reductive deprotonation is presented as a new reaction sequence in gold chemistry.

Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

Gabriele Agonigi
Investigation
;
2017

Abstract

The synthesis and characterization of hitherto hypothetical AuIIIπ-alkyne complexes is reported. Bonding and stability depend strongly on the trans effect and steric factors. Bonding characteristics shed light on the reasons for the very different stabilities between the classical alkyne complexes of PtIIand their drastically more reactive AuIIIcongeners. Lack of back-bonding facilitates alkyne slippage, which is energetically less costly for gold than for platinum and explains the propensity of gold to facilitate C−C bond formation. Cycloaddition followed by aryl migration and reductive deprotonation is presented as a new reaction sequence in gold chemistry.
Rocchigiani, Luca; Fernandez-Cestau, Julio; Agonigi, Gabriele; Chambrier, Isabelle; Budzelaar, Peter H. M.; Manfred Bochmann, And
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/932074
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