title: Structure, stability, and nature of bonding in carbon monoxide bound EX3+ complexes (E = group 14 element; X = H, F, Cl, Br, I).
abstract: A density functional theory study is performed to predict the structures and stability of carbon monoxide (CO) bound EX3+ (E = C, Si, Ge, Sn, Pb; X = H, F, Cl, Br, I) complexes. The possibility of bonding through both C- and O-sides of CO is considered. Thermochemical analysis reveals that all the dissociation processes producing CO and EX3+ are endothermic in nature whereas most of the dissociation reactions are endergonic in nature at room temperature. The nature of bonding in EC/O bonds is analyzed via Wiberg bond index, natural population analysis, electron density, and energy decomposition analyses in conjunction with natural orbitals for chemical valence scheme. In comparison to CO stretching frequency ( ν∼CO) in free CO, while a red shift is noted in O-side binding, the C-side binding results in a blue shift in ν∼CO. The relative change in ν∼CO values in CO bound EX3+ complexes on changing either E or X is scrutinized and possible explanation is provided in terms of polarization in the σ- and π-orbitals and the relative strength of C→E or O→E σ-donation and E→C or E→O π-back-donation. © 2016 Wiley Periodicals, Inc.
authors.affiliation: Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology, Kharagpur, 721302, India.
authors.forename: Manas
authors.initials: M
authors.lastname: Ghara
authors.affiliation: Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology, Kharagpur, 721302, India.
authors.forename: Sudip
authors.initials: S
authors.lastname: Pan
authors.affiliation: Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology, Kharagpur, 721302, India.|Department of Chemistry, Indian Institute of Science Education and Research, Pune, Maharashtra, 411008, India.
authors.forename: Anand
authors.initials: A
authors.lastname: Kumar
authors.affiliation: Departamento De Física Aplicada, Centro De Investigación Y De Estudios Avanzados Unidad Mérida, Km 6 Antigua Carretera a Progreso. Apdo. Postal 73, Cordemex, Mérida, Yuc, 97310, México.
authors.forename: Gabriel
authors.initials: G
authors.lastname: Merino
authors.affiliation: Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology, Kharagpur, 721302, India.
authors.forename: Pratim K
authors.initials: PK
authors.lastname: Chattaraj
keywords: density functional theory; energy decomposition analysis; stretching frequency; σ-donation and π-back-donation