期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 131, 期 36, 页码 12872-+出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja904370h
关键词
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资金
- National Science Foundation [CHE-0615274, CHE-0741936]
- Department of Education
- Basic Energy Sciences, Department of Energy [DEFG02-03ER15387]
1-Adamantyl- and mesitylazide react with (dtbpe)Ni=CPh2 (1; dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) at ambient temperature to give the ketimines RN=CPh2 (2a, R = Mes; 2b, R = Ad) in high yield. Kinetic studies for the reaction of 1 with N(3)Ad yield activation parameters of Delta H double dagger = +8(+/- 1) kcal/mol and Delta S double dagger = -44(+/- 3) cat/(mol.K). Treatment of 1 with N2O at low temperature results in clean conversion to the benzophenone complex (dtbpe)Ni(eta(2)-OCPh2) (5) upon elimination of N-2. The nickel-imido complexes (dtbpe)Ni=NR (4a, R = Mes; 4b, R = Ad) react with N(3)Mes and N3Ad at ambient temperature to give the diazenes RN=NR (6a, R = Mes; 6b, R = Ad) in good yield. B3LYP/6-311+G(d) calculations support a mechanism for all three reactions that features 1,3-dipolar cycloaddition to give five-membered ring (Huisgen) intermediates, followed by NZ elimination to give the products. Calculated activation parameters for the reaction of (dhpe)Ni=CH2 (dhpe = 1,2-bis(dihydridophosphino)ethane) with N3Me compare well with the experimental values.
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