Formation and infrared spectroscopic characterization of carbon suboxide complexes TM‐η1‐C3O2 and the inserted ketenylidene complexes OCTMCCO (TM=Cu, Ag, Au) in solid neon. Issue 3 (7th February 2022)

• Record Type: Journal Article
• Authors: Li, Hongmin; Zhou, Yangyu; Wang, Guanjun; Zeng, Xiaoqing; Zhou, Mingfei
• Is Part Of: Journal of computational chemistry. Volume 44:Issue 3(2023)
• Page Start: 129
• Page End: 137
• Publication Date: 2022-02-07
• Subjects: carbon suboxide -- IR spectroscopy -- ketenylidene complexes -- matrix isolation -- quantum chemical calculations; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.26817
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract: The reactions of coinage metal atoms Cu, Ag and Au with carbon suboxide (C3 O2 ) are studied by matrix isolation infrared spectroscopy. The weakly bound complexes TM‐ η 1 ‐C3 O2 (TM=Cu, Ag, Au), in which the carbon suboxide ligand binds to the metal center in the monohapto fashion are formed as initial reaction products. The complexes subsequently isomerize to the inserted products OCTMCCO upon visible light ( λ = 400–500 nm) excitation. The analysis of the electronic structure using modern quantum chemistry methods suggests that the linear OCTMCCO complexes are best described by the bonding interactions between the TM + cation in the electronic singlet ground state and the [OC…CCO] − ligands in the doublet state forming two TM + ← ligands σ donation and two TM + → ligands π backdonation bonding components. In addition, the CuCCO, AgCCO and AuCCO complexes are also formed, which are predicted to be bent. Abstract : Infrared spectroscopic investigations on the reactions of copper, silver, and gold atoms with carbon suboxide in solid neon matrix show that the weakly bound complexes TM‐ η 1 ‐C3 O2 (TM=Cu, Ag, Au) are initially formed. The complexes convert into the ketenylidene complexes OCTMCCO under visible light excitation. The OCTMCCO complexes are predicted to be linear and are best described by the bonding interactions between a TM + cation in the electronic singlet ground state 1 S and the [OC…CCO] − ligands in the doublet state with the unpaired electron in the π orbital of CCO − .