title: Comparative study of the hydrogen-bonded complexes of phenol and o-cyanophenol with CO Ab initio and DFT approachs.
abstract: The structures, stability and vibrational spectra of the hydrogen-bonded complexes of carbon monoxide (CO) with phenol and o-cyanophenol (syn and anti) have been studied using ab initio and DFT calculations. Full geometry optimization has been performed for the studied complexes by DFT (BLYP/6-311++G(d,p)) calculations. The calculations show that the hydrogen-bond formation of carbon monoxide (CO) with phenol and o-cyanophenol (syn and anti) leads to the following stable structures: C6H5OH...CO (1A); C6H5OH...OC (1B); (syn) o-CNC6H4OH...CO (2A-syn); (syn) o-CNC6H4OH...OC (2B-syn); (anti) o-CNC6H4 OH...CO (2A-anti) and (anti) o-CNC6H4OH...OC (2B-anti). Having in mind the corrected values of the dissociation energy, the studied hydrogen-bonded complexes can be ordered according their stability as follows: 2A-anti>2A-syn>1A>2B-anti>1B>2B-syn. The predicted red-shifts for the nuOH vibration with the B3LYP/6-311++G(d,p) calculations for the structures 1A (-46 cm-1), 2A-syn (-60 cm-1) and 2A-anti (-73 cm-1) are in very good agreement with the experimentally observed. The magnitudes of the wavenumber shifts are indicative of relatively weak OH...C hydrogen-bonded interactions. The calculations predict an increase of the IR intensity of the nuOH vibration in the complexes 1A, 2A-anti and 2A-syn up to five times.
authors.affiliation: Institute of Organic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Bl. 9, 1113, Sofia, Bulgaria. dimj@srv.orgchm.bas.bg
authors.forename: Yordanka
authors.initials: Y
authors.lastname: Dimitrova
authors.forename: Lalka I
authors.initials: LI
authors.lastname: Daskalova
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D009570:Nitriles / Q000737:chemistry*; D019800:Phenol / Q000737:chemistry*
chemical_list: D009570:Nitriles; D019800:Phenol; D002248:Carbon Monoxide