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Formation of Metal Oxyfluorides from Specific Metal Reactions with Oxygen Difluoride: Infrared Spectroscopic and Theoretical Investigations of the OScF 2 Radical and OScF with Terminal Single and Triple ScO Bonds
Author(s) -
Gong Yu,
Andrews Lester,
Bauschlicher Charles W.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201005
Subject(s) - chemistry , scandium , lone pair , triple bond , molecule , unpaired electron , crystallography , photochemistry , density functional theory , single bond , bond length , computational chemistry , inorganic chemistry , double bond , alkyl , organic chemistry , polymer chemistry
The scandium oxydifluoride free radical, OScF 2 , is produced by the spontaneous, specific reaction of laser ablated Sc atoms with OF 2 in solid argon and characterized by using matrix infrared spectroscopy and theoretical calculations. The OScF 2 molecule is predicted to have C 2 v symmetry and a 2 B 2 ground state with an unpaired electron located primarily on the terminal oxygen atom, which makes it a scandium difluoride molecule coordinated by a neutral oxygen atom radical in forming the ScO single bond. The closed shell singlet OScF molecule with an obtuse bent geometry has a much shorter ScO bond of 1.682 Å than that of the OScF 2 radical (1.938 Å) on the basis of B3LYP calculations. The ScO bond in OScF consists of two covalent bonds and a dative bond in which the oxygen 2p π lone pair donates electron density into an empty Sc 3d orbital thus forming a triple oxo bond. Density functional calculations suggest it is highly exothermic for fluorine transfer from OF 2 to scandium, which favors the formation of the OScF 2 radical species as well as the OScF molecule after fluorine loss.