Reductive Coupling and Loss of N2 from Magnesium Diazomethane Derivatives

Abstract

The reductive coupling of two diazomethanes is affected by reaction with [(NacNacMes )Mg]2 affording the species [(NacNacMes )Mg(N2 CPh2 )]2 2 and [(NacNacMes )Mg(N2 C(C6 H4 )2 )]2 3. These species containing N4 linkages readily evolve the central N2 at 50 and 75 °C to give the Mg-imide products [(NacNacMes )Mg(NCPh2 )]2 (4) and [(NacNacMes )Mg(NC(C6 H4 )2 )]2 (5), respectively. The mechanism for the loss of N2 was considered computationally. Compounds 2 and 3 reacted with O2 to liberate the tetrazene (Ph2 N2 )2 6 and the hydrazine ((C6 H4 )2 CN)2 7, whereas reactions with Me3 SiOSO2 CF3 or Me3 SiCl with 2 and 3 provide the related silyl imines 8 and 9, respectively.