Carbon Monoxide Bonding With BeO and BeCO3: Surprisingly High CO Stretching Frequency of OCBeCO3. Issue 1 (4th November 2014)

• Record Type: Journal Article
• Authors: Chen, Mohua; Zhang, Qingnan; Zhou, Mingfei; Andrada, Diego M.; Frenking, Gernot
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 1(2015)
• Page Start: 124
• Page End: 128
• Publication Date: 2014-11-04
• Subjects: beryllium carbonate -- bonding analysis -- carbonyl complexes -- donor–acceptor interactions -- matrix isolation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201406264
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The complexes OCBeCO3 and COBeCO3 have been isolated in a low‐temperature neon matrix. The more stable isomer OCBeCO3 has a very high CO stretching mode of 2263 cm −1, which is blue‐shifted by 122 cm −1 with respect to free CO and 79 cm −1 higher than in OCBeO. Bonding analysis of the complexes shows that OCBeO has a stronger OCBeY bond than OCBeCO3 because it encounters stronger π backdonation. The isomers COBeCO3 and COBeO exhibit red‐shifted CO stretching modes with respect to free CO. The inverse change of CO stretching frequency in OCBeY and COBeY is explained with the reversed polarization of the σ and π bonds in CO. Abstract : The carbonyl complex OC→BeCO3 has been isolated in a neon matrix. The CO stretching frequency exhibits a very strong blueshift with respect to free CO that is much higher than in OC→BeO although the donor–acceptor bond is significantly weaker. This is explained with the help of a quantum chemical bonding analysis, which also rationalizes the redshifts of the isomers OC→BeCO3 and OC→BeO.