title: Reactions of gadolinium atoms and dimers with CO: formation of gadolinium carbonyls and photoconversion to CO activated molecules.
abstract: Reactions of gadolinium atoms and dimers with carbon monoxide molecules in solid argon have been studied using matrix isolation infrared absorption spectroscopy. Mononuclear Gd(CO)x (x = 1-3) and dinuclear Gd2(CO)x (x = 1, 2) gadolinium carbonyls formed spontaneously on annealing. The Gd(CO)x complexes are CO terminal-bonded carbonyls, whereas the Gd2CO and Gd2(CO)2 carbonyl complexes were characterized to have asymmetrically bridging and side-on-bonded CO, which are drastically activated with remarkably low C-O stretching frequencies. The cyclic Gd2(mu-C)(mu-O) and Gd3(mu-C)(mu-O) molecules in which the C-O triple bond is completely cleaved were also formed on annealing. The Gd2(CO)2 complex rearranged to the more stable c-Gd2(mu-O)(mu-CCO) isomer, which also has a four-membered ring structure with one CO being completely activated.
authors.affiliation: Department of Chemistry & Laser Chemistry Institute, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, P. R. China.
authors.forename: Xi
authors.initials: X
authors.lastname: Jin
authors.forename: Ling
authors.initials: L
authors.lastname: Jiang
authors.forename: Qiang
authors.initials: Q
authors.lastname: Xu
authors.forename: Mingfei
authors.initials: M
authors.lastname: Zhou