Gold Complexes with ADAP Ligands: Effect of Bulkiness in Catalytic Carbene Transfer Reactions (ADAP = Alkoxydiaminophosphine)

A family of gold(I) complexes of composition AuCl(ADAP) (ADAP = alkoxydiaminophosphine) has been synthetized through a one-pot simple protocol in which the ADAP ligand is prepared in situ before reaction with the Au(I) source. Structural data demonstrate that these ADAP ligands exert a trans effect...

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Bibliographic Details
Authors: Pizarro, Juan Diego, Molina González, Francisco, Romero Fructos-Vázquez, Manuel, Pérez Romero, Pedro José
Format: article
Publication Date:2020
Country:España
Institution:Universidad de Huelva (UHU)
Repository:Arias Montano. Repositorio Institucional de la Universidad de Huelva
Language:English
OAI Identifier:oai:ariasmontano.uhu.es:10272/18912
Online Access:http://hdl.handle.net/10272/18912
Access Level:Open access
Keyword:Functionalization
Carbene compounds
Hydrocarbons
Gold
Ligands
Description
Summary:A family of gold(I) complexes of composition AuCl(ADAP) (ADAP = alkoxydiaminophosphine) has been synthetized through a one-pot simple protocol in which the ADAP ligand is prepared in situ before reaction with the Au(I) source. Structural data demonstrate that these ADAP ligands exert a trans effect superior to those of phosphine or phosphite ligands. Evaluation of the buried volume (%VBur) indicates a steric hindrance higher than those of several NHC, PR3, and P(OR3) ligands, in the context of AuCl(L) complexes. These complexes promote the catalytic transfer of a carbene group from ethyl diazoacetate to alkenes and alkanes. In the case of styrene, both the Csp2−H bonds and the CC bond are functionalized, the relative ratio depending on the catalyst employed and correlating well with the %VBur value. Data available allow proposing that these compounds display quite similar electronic properties but differ in steric properties, a variable that can be readily controlled upon modifying the alkoxy group at the ADAP ligand by simply replacing the starting alcohol employed in the synthesis.