Dinitrogen Bridged Gold Clusters

A family of dinitrogen complexes, [(LAu) 6 (N 2 )] 2+ (L = a phosphine), with the dinitrogen unit bridging two clusters of three gold atoms have been prepared from hydrazine and [(LAu) 3 (O)] + . Structural characterization of the PPh 2 i Pr (Ph, phenyl; i Pr, isopropyl) derivative shows a nitrogen-nitrogen single-bond distance indicative of hydrazido (N 2 4− ) character for the dinitrogen unit. The complexes can be reduced and protonated to give low [13% when L = PPh 2 Me (Me, methyl)] to quantitative [100% when L = P( p -MeOC 6 H 5 ) 3 ] yields of ammonia, establishing that bonding of dinitrogen to six metal atoms can lead to facile cleavage of the nitrogen-nitrogen bond.