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CO Oxidation by Group 3 Metal Monoxide Cations Supported on [Fe(CO) 4 ] 2−
Author(s) -
Chi Chaoxian,
Qu Hui,
Meng Luyan,
Kong Fanchen,
Luo Mingbiao,
Zhou Mingfei
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201707898
Subject(s) - chemistry , heteronuclear molecule , photodissociation , carbon monoxide , valence (chemistry) , ion , metal , crystallography , infrared spectroscopy , inorganic chemistry , photochemistry , nuclear magnetic resonance spectroscopy , stereochemistry , catalysis , biochemistry , organic chemistry
Infrared photodissociation spectroscopy of mass‐selected heteronuclear cluster anions in the form of OMFe(CO) 5 − (M=Sc, Y, La) indicates that all these anions involve an 18‐electron [Fe(CO) 4 ] 2− building block that is bonded with the M center through two bridged carbonyl ligands. The OLaFe(CO) 5 − anion is determined to be a CO‐tagged complex involving a [Fe(CO) 4 ] 2− [LaO] + anion core. In contrast, the OYFe(CO) 5 − anion is characterized to have a [Fe(CO) 4 ] 2− [Y(η 2 ‐CO 2 )] + structure involving a side‐on bonded CO 2 ligand. The CO‐tagged complex and the [Fe(CO) 4 ] 2− [Sc(η 2 ‐CO 2 )] + isomer co‐exist for the OScFe(CO) 5 − anion. These observations indicate that both the ScO + and YO + cations supported on [Fe(CO) 4 ] 2− are able to oxidize CO to CO 2 . Theoretical analyses show that [Fe(CO) 4 ] 2− coordination significantly weakens the MO + bond and decreases the energy gap of the interacting valence orbitals between MO + and CO, leading to the CO oxidation reactions being both thermodynamically exothermic and kinetically facile.