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Vanga, Mukundam; Muñoz‐Castro, Alvaro; Dias, H. V. Rasika
Chemistry : a European journal, January 22, 2024, Letnik: 30, Številka: 5Journal Article
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. 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.
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