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On the mechanisms of carbon monoxide reduction with zirconium hydrides

Journal Article · · Acc. Chem. Res.; (United States)
DOI:https://doi.org/10.1021/ar50148a004· OSTI ID:5400723
Results of studies to prepare dinitrogen complexes of zirconium led to the synthesis of a crystalline N/sub 2/ adduct of bis(pentamethylcyclopentadienyl)zirconium, ((eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/ZrN/sub 2/)/sub 2/N/sub 2/(1), which when treated with CO yielded sequentially ((eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(CO))/sub 2/N/sub 2/ and (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(CO)/sub 2/. Reaction of the latter compound with H/sub 2/ was found to proceed according to the reaction (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(CO)/sub 2/ + H/sub 2/ ..-->.. (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(H)(OCH/sub 3/) + CO (2 atm, 110/sup 0/C). Results of studies of the mechanisms of this reaction are reported. Olefins, acetylenes, nitriles, isocyanides, and H/sub 2/, as well as CO, rapidly displace the N/sub 2/ in 1 to yield a variety of stable adducts. Possible mechanisms for these related reactions are also suggested. (BLM)
Research Organization:
California Inst. of Tech., Pasadena
OSTI ID:
5400723
Journal Information:
Acc. Chem. Res.; (United States), Journal Name: Acc. Chem. Res.; (United States) Vol. 13:4; ISSN ACHRE
Country of Publication:
United States
Language:
English