期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 22, 期 7, 页码 2376-2385出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201504475
关键词
donor-acceptor interactions; IR photodissociation spectroscopy; main-group carbonyls; matrix isolation; quantum chemical calculations
资金
- Ministry of Science and Technology of China [2013CB834603, 2012YQ220113-3]
- National Natural Science Foundation of China [21433005]
- Deutsche Forschungsgemeinschaft [FR 641/25-2]
A combined experimental and theoretical study on the main-group tricarbonyls [B(CO)(3)] in solid noble-gas matrices and [C(CO)(3)](+) in the gas phase is presented. The molecules are identified by comparing the experimental and theoretical IR spectra and the vibrational shifts of nuclear isotopes. Quantum chemical ab initio studies suggest that the two isoelectronic species possess a tilted (1)((1)-CO)-bonded carbonyl ligand, which serves as an unprecedented one-electron donor ligand. Thus, the central atoms in both complexes still retain an 8-electron configuration. A thorough analysis of the bonding situation gives quantitative information about the donor and acceptor properties of the different carbonyl ligands. The linearly bonded CO ligands are classical two-electron donors that display classical sigma-donation and -back-donation following the Dewar-Chatt-Duncanson model. The tilted CO ligand is a formal one-electron donor that is bonded by sigma-donation and -back-donation that involves the singly occupied orbital of the radical fragments [B(CO)(2)] and [C(CO)(2)](+).
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