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Reductive Coupling and Loss of N 2 from Magnesium Diazomethane Derivatives
Author(s) -
Zhou Jiliang,
Liu Liu Leo,
Cao Levy L.,
Stephan Douglas W.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201802138
Subject(s) - diazomethane , chemistry , magnesium , hydrazine (antidepressant) , medicinal chemistry , silylation , organic chemistry , catalysis , chromatography
The reductive coupling of two diazomethanes is affected by reaction with [(NacNac Mes )Mg] 2 affording the species [(NacNac Mes )Mg(N 2 CPh 2 )] 2 2 and [(NacNac Mes )Mg(N 2 C(C 6 H 4 ) 2 )] 2 3 . These species containing N 4 linkages readily evolve the central N 2 at 50 and 75 °C to give the Mg–imide products [(NacNac Mes )Mg(NCPh 2 )] 2 ( 4 ) and [(NacNac Mes )Mg(NC(C 6 H 4 ) 2 )] 2 ( 5 ), respectively. The mechanism for the loss of N 2 was considered computationally. Compounds 2 and 3 reacted with O 2 to liberate the tetrazene (Ph 2 N 2 ) 2 6 and the hydrazine ((C 6 H 4 ) 2 CN) 2 7 , whereas reactions with Me 3 SiOSO 2 CF 3 or Me 3 SiCl with 2 and 3 provide the related silyl imines 8 and 9 , respectively.