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Carbon monoxide-induced N-N bond cleavage of nitrous oxide that is competitive with oxygen atom transfer to carbon monoxide as mediated by a Mo(II)/Mo(IV) catalytic cycle.

Authors
Type
Published Article
Journal
Journal of the American Chemical Society
1520-5126
Publisher
American Chemical Society
Publication Date
Volume
133
Issue
46
Pages
18602–18605
Identifiers
DOI: 10.1021/ja208669s
PMID: 22026748
Source
Medline

Abstract

In the presence of CO, facile N-N bond cleavage of N(2)O occurs at the formal Mo(II) center within coordinatively unsaturated mononuclear species derived from Cp*Mo[N((i)Pr)C(Me)N((i)Pr)](CO)(2) (Cp* = η(5)-C(5)Me(5)) (1) and {Cp*Mo[N((i)Pr)C(Me)N((i)Pr)]}(2)(μ-η(1):η(1)-N(2)) (9) under photolytic and dark conditions, respectively, to produce the nitrosyl, isocyanate complex Cp*Mo[N((i)Pr)C(Me)N((i)Pr)](κ-N-NO)(κ-N-NCO) (7). Competitive N-O bond cleavage of N(2)O proceeds under the same conditions to yield the Mo(IV) terminal metal oxo complex Cp*Mo[N((i)Pr)C(Me)N((i)Pr)](O) (3), which can be recycled to produce more 7 through oxygen-atom-transfer oxidation of CO to produce CO(2).

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