Classical Gold Carbonyl Complexes in Tetrahedral and Trigonal-Planar Settings
Dr. Mukundam Vanga
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019 United States
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Prof. Dr. Alvaro Muñoz-Castro
Facultad de Ingeniería, Arquitectura y Diseño, Universidad San Sebastián, Bellavista 7, Santiago, 8420524 Chile
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Prof. Dr. H. V. Rasika Dias
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019 United States
Search for more papers by this authorDr. Mukundam Vanga
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019 United States
Search for more papers by this authorCorresponding Author
Prof. Dr. Alvaro Muñoz-Castro
Facultad de Ingeniería, Arquitectura y Diseño, Universidad San Sebastián, Bellavista 7, Santiago, 8420524 Chile
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Prof. Dr. H. V. Rasika Dias
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019 United States
Search for more papers by this authorGraphical Abstract
Pyridyl-borate scorpionates decorated with anionic and fluoro-alkyl groups serve as ideal ligands to capture gold(I)-carbon monoxide fragments in trigonal planar and tetrahedral environments that display remarkably low C−O stretching frequencies, and have significant Au−CO π-bond character.
Abstract
A unique four-coordinate, classical gold(I)-carbonyl complex with substantial backdonation from gold has been isolated by using a B-methylated and fluorinated tris(pyridyl)borate chelator. Its lighter silver(I) and copper(I) analogs enabled a study of trends in the coinage-metal family. The B-arylated ligand version also afforded a gold–carbon monoxide complex that displays a notably low C−O stretch value, but with trigonal planar geometry at the gold. A computational analysis shows that the AuI−CO bonds of these tris(pyridyl)borate ligand-supported molecules consist of electrostatic attraction, OC→Au σ-donation, and very significant Au→CO π-back-bonding components. The latter is responsible for the observed C−O stretching frequencies, which are lower than in free CO.
Conflict of interest
There are no conflicts to declare.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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