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Cleavage of SO sub 2 on (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 Mo sub 2 (. mu. -S sub 2 )(. mu. -S) sub 2 to form S sub 8 and a thiosulfate complex, (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 Mo sub 2 (. mu. -S sub 2 )(. mu. -S)(. mu. -SSO sub 3 ). Possible role in homogeneous hydrogenation of SO sub 2 catalyzed by Mo-S complexes

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00202a024· OSTI ID:6707992
Reaction of SO{sub 2} with solutions of Cp*{sub 2}Mo{sub 2}({mu}-S{sub 2})({mu}-S){sub 2} (1) initially yields 1-SO{sub 2}, which is shown by crystallography to contain an SO{sub 2} weakly bound to a {mu}-S (S-S = 2.60 {angstrom}). SO{sub 2} further reacts with 1-SO{sub 2} to quantitatively give Cp*{sub 2}Mo{sub 2{minus}} ({mu}-S{sub 2})({mu}-S)({mu}-SSO{sub 3}) (2), which now contains an SO{sub 3} bound to the {mu}-S (S-S = 2.17 {angstrom}). Effectively, a {mu}-S{sub 2}O{sub 3} (thiosulfate) ligand is formed by an oxygen-transfer process, and the source of the oxygen as established by {sup 18}O labeling is SO{sub 2}. S{sub 8} is also produced, showing that SO{sub 2} has undergone net disproportionation to SO{sub 3} and S{sub 8}.
OSTI ID:
6707992
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:20; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English