New Mono-Dinitrogen Complexes of Molybdenum That Produce Ammonia and Hydrazine

Article abstract of DOI:10.1021/ja00304a020

A new, extensive series of mono-N2 complexes of molybdenum is reported.The sodium amalgam reduction of MoCl3(triphos), where triphos=PhP(CH2CH2PPh2)2, in tetrahydrofuran solution in the presence of 2L or L2 and with a deficiency of N2 led to the formation of Mo(N2)(triphos)(L2) (1A-F): 1A, L2=2 PPhMe2; 1B, L2=Me2PCH2PMe2; 1C, L2=1,2-(Me2As)2C6H4; 1D, L=Ph2PCH2PPh2; 1E, L2=Ph2PCH2CH2PPh2; 1F, L2=1,1'-(Ph2PC5H4)2Fe, DPPFe.Complexes 1C and 1E were each a mixture of isomeric mono-N2 complexes.Complex 1F was isolated together with Mo(triphos)(η²-DPPFe)(η¹-DPPFe).Complexes 1A-F all reacted with HBr in CH2Cl2 to afford ammonia, hydrazine, and N2 (and some H2) in varying yields.The highest yield of ammonia was obtained from 1F, and the highest yield of hydrazine was obtained from 1A (HCl/toluene at 70 deg C).