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Strong Metallophilic Interactions in the Palladium Arylation by Gold Aryls


  • We thank the Spanish Ministerio de Ciencia e Innovación (INTECAT Consolider Ingenio-2010 CSD2006-0003; CTQ2010-18901/BQU; CTQ2008-06647-C02-01; CTQ2009-14186/C02-01) and the Junta de Castilla y León (VA281A11-2 and VA373A11-2) for financial support; CESGA for generous allocation of computational resources; and Dr. José M. Aurrecoechea (Universidad del País Vasco) for discussions.


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It's the second step that counts: Arylation of Pd by Au takes place through transition states and intermediates featuring strong Au⋅⋅⋅Pd metallophilic interactions (see picture). However, the aryl transfer from [AuArL] to [PdArClL2] is thermodynamically disfavored and will not occur unless an irreversible Ar[BOND]Ar coupling from [PdAr2L2] follows.

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