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Formation of MgO-Supported Manganese Carbonyl Complexes by Chemisorption of Mn(CO)5CH3

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School of Chemistry, Institute of Science, Suranaree University of Technology, Nakhon Ratchasima, Thailand 30000
Department of Chemical Engineering and Materials Science and §Department of Chemistry, University of California, Davis, California 95616, United States
*E-mail: [email protected] (J.W.); [email protected] (B.C.G.).
Cite this: Langmuir 2013, 29, 21, 6279–6286
Publication Date (Web):April 24, 2013
https://doi.org/10.1021/la303269h
Copyright © 2013 American Chemical Society

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    Abstract

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    MgO-supported manganese carbonyl complexes were prepared by chemical vapor deposition of Mn(CO)5CH3 on partially dehydroxylated, high-area MgO powder. X-ray absorption spectra identify the resultant surface species, on average, as Mn(CO)4(Os)2 (where the two oxygen ligands are part of the MgO surface), and infrared spectra show that the chemisorption results from the reaction of Mn(CO)5CH3 with OH groups of the MgO surface. Electron paramagnetic resonance and X-ray absorption near edge data indicate that the manganese was in a positive oxidation state other than +2, but the value is not determined, and the IR spectra indicate the presence of a mixture of manganese carbonyls. Extended X-ray absorption fine structure spectra determine the average Mn–CO bond distance to be 1.87 Å and the average Mn–O bond distance to be 2.12 Å. The surface complex was found to be stable in O2 at room temperature.

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