Lewis Acid-Induced Dinitrogen Cleavage in an Anionic Side-on End-on Bound Dinitrogen Diniobium Hydride Complex

The side-on end-on dinitrogen hydride complex [{Na(dme)}(2){(O(3))Nb}(2)(μ-η(1):η(2)-N(2))(μ-H)(2)] (3-Na, [O(3)](3−) = [(3,5-(t)Bu(2)-2-O-C(6)H(2))(3)CH](3−)) was observed to undergo facile elimination of H(2) and cleavage of the N–N bond in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN), AlMe(3), and ZnMe(2). Treatment of 3-Na with 9-BBN and ZnMe(2) afforded the nitride complex [{K(dme)(2)}(2){(O(3))Nb}(2)(μ-N)(2)] (2-Na). The reaction of 3-Na with AlMe(3) afforded [{Na(dme)}(2){(O(3))AlMe}(2)(NbMe(2))(2)(μ-N)(2)] (5). The nitride complex 2-Na was treated with 9-BBN and AlMe(3) to form [{Na(dme)}(2){(O(3))Nb}(μ-NH)(μ-NBC(8)H(14)){Nb(O(3)C)}] (4) and 5, respectively. Complex 2-Na, 4, and 5 were structurally characterized.