Jellyfish-type Dinuclear Hafnium Azido Complexes: Synthesis and Reactivity.

Di- and multinuclear hafnium complexes bridged by ligands have been rarely reported. In this article, a novel 3,5-disubstituted pyrazolate-bridged ligand LH with two [N N] -type chelating side arms was designed and synthesized, which supported a series of dinuclear hafnium complexes. Dinuclear hafnium azides [LHf (μ-1,1-N ) (N ) ][Na(THF) ] 3 and [LHf (μ-1,1-N ) (N ) ][Na(2,2,2-Kryptofix)] 4 were further synthesized and structurally characterized, featuring two sets of terminal and bridging azido ligands like jellyfishes.

Direct Incorporation of Dinitrogen into an Aliphatic C-H Bond.

The activation of dinitrogen (N) and direct incorporation of its N atom into C-H bonds to create aliphatic C-N compounds remains unresolved. Incompatible conditions between dinitrogen reduction and C-H functionalization make this process extremely challenging. Herein, we report the first example of dinitrogen insertion into an aliphatic C-H bond on the ligand scaffold of a 1,3-propane-bridged [NN]-type dititanium complex.

(-Bu)NBr-Promoted N Splitting to Molybdenum Nitride.

Splitting of N via six-electron reduction and further functionalization to value-added products is one of the most important and challenging chemical transformations in N fixation. However, most N splitting approaches rely on strong chemical or electrochemical reduction to generate highly reactive metal species to bind and activate N, which is often incompatible with functionalizing agents. Catalytic and sustainable N splitting to produce metal nitrides under mild conditions may create efficient and straightforward methods for N-containing organic compounds.

Synthesis of arylamines and N-heterocycles by direct catalytic nitrogenation using N.

Ammonia and nitric acid are two key platform chemicals to introduce nitrogen atoms into organic molecules in chemical industry. Indeed, nitric acid is mostly produced through the oxidation of ammonia. The ideal nitrogenation would involve direct use of dinitrogen (N) as a N source to construct N-containing organic molecules.

Silylamido supported dinitrogen heterobimetallic complexes: syntheses and their catalytic ability.

Molybdenum dinitrogen complexes supported by monodentate arylsilylamido ligand, [Ar(MeSi)N]MoNMg(THF)[N(SiMe)Ar] () and [Ar(MeSi)N]MoNSiMe () (Ar = 3,5-MeCH) were synthesized and structurally characterized, and proved to be effective catalysts for the disproportionation of cyclohexadienes and isomerization of terminal alkenes. The H NMR spectrum suggested that the bridging nitrogen ligand remains intact during the catalytic reaction, indicating possible catalytic ability of the Mo-N=N motif.

Ni-Catalyzed Cross-Coupling of Dimethyl Aryl Amines with Arylboronic Esters under Reductive Conditions.

Herein, we reported a successful Suzuki-Miyaura coupling of dimethyl aryl amines to forge biaryl skeleton via Ni catalysis in the absence of directing groups and preactivation. This transformation proceeded with high efficiency in the presence of magnesium. Preliminary mechanism studies demonstrated dual roles of magnesium: (i) a reductant that reduced Ni(II) species to active Ni(I) catalyst; (ii) a unique promoter that facilitated the Ni(I)/Ni(III) catalytic cycle.