title: Observation of Main-Group Tricarbonyls [B(CO)3 ] and [C(CO)3 ](+) Featuring a Tilted One-Electron Donor Carbonyl Ligand.
abstract: 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 η(1) (μ1 -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 σ-donation and π-back-donation following the Dewar-Chatt-Duncanson model. The tilted CO ligand is a formal one-electron donor that is bonded by σ-donation and π-back-donation that involves the singly occupied orbital of the radical fragments [B(CO)2 ] and [C(CO)2 ](+) .
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.
authors.forename: Jiwen
authors.initials: J
authors.lastname: Jian
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.
authors.forename: Jiaye
authors.initials: J
authors.lastname: Jin
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.
authors.forename: Hui
authors.initials: H
authors.lastname: Qu
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.
authors.forename: Hailu
authors.initials: H
authors.lastname: Lin
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.
authors.forename: Mohua
authors.initials: M
authors.lastname: Chen
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China.
authors.forename: Guanjun
authors.initials: G
authors.lastname: Wang
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, P. R. China. mfzhou@fudan.edu.cn.
authors.forename: Mingfei
authors.initials: M
authors.lastname: Zhou
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043, Marburg, Germany.
authors.forename: Diego M
authors.initials: DM
authors.lastname: Andrada
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043, Marburg, Germany.
authors.forename: Markus
authors.initials: M
authors.lastname: Hermann
authors.affiliation: Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043, Marburg, Germany. frenking@chemie.uni-marburg.de.
authors.forename: Gernot
authors.initials: G
authors.lastname: Frenking
keywords: IR photodissociation spectroscopy; donor-acceptor interactions; main-group carbonyls; matrix isolation; quantum chemical calculations