Titanium‐Promoted Dinitrogen Cleavage, Partial Hydrogenation, and Silylation

Abstract

Sauber getrennt: Die Reduktion eines dreiwertigen Titankomplexes führte unter N‐N‐Spaltung zu einem Titan(IV)‐Nitridkomplex (siehe Struktur), der anschließend silyliert werden konnte.

Structure and Reactivity of a Hafnocene μ‐Nitrido Prepared From Dinitrogen Cleavage

“…The six‐electron cleavage of molecular nitrogen by soluble metal complexes to form either terminal1 or bridging nitrido2 compounds is an attractive transformation for developing synthetic routes to organic molecules using N 2 as the nitrogen source 3. Acylation,4 silylation,5 alkylation6 and hydrogenation7 have all been identified as viable strategies to construct new bonds to metal–nitrido complexes following N 2 cleavage. Despite numerous examples in Groups 5 and 6, to our knowledge, a Group 4 transition metal nitrido complex has not been isolated following N 2 cleavage.…”

Unusually Strong Binding of Dinitrogen to a Ruthenium Center

“…Despite the prominence of iron systems in catalyzing the reduction of dinitrogen in industrial and biological contexts, [1, 2a, 3, 5, 6] and important recent advances in dinitrogen fixation by iron complexes, [1,7] early-and mid-transition metal complexes have shown greatest promise to date in cleaving the NÀN bond. [1][2][3][8][9][10][11] A benchmark was set by Yandulov and Schrock, who reported molybdenum triamidoamine derivatives, the first welldefined catalysts capable of selectively reducing N 2 to ammonia.[12] Late-metal complexes tend to be limited by the lower energy of their d orbitals (which impedes back-donation into the high-energy NN antibonding orbitals), [13,14] and high N 2 lability. The latter has been identified as a key barrier to the development of late-metal catalysts for N 2 activation.…”