Vanadium-Catalyzed Dinitrogen Reduction to Ammonia via a [V]═NNH2 Intermediate.

The catalytic transformation of N2 to NH3 by transition metal complexes is of great interest and importance but has remained a challenge to date. Despite the essential role of vanadium in biological N2 fixation, well-defined vanadium complexes that can catalyze the conversion of N2 to NH3 are scarce. In particular, a V(NxHy) intermediate derived from proton/electron transfer reactions of coordinated N2 remains unknown. Here, we report a dinitrogen-bridged divanadium complex bearing POCOP (2,6-(tBu2PO)2-C6H3) pincer and aryloxy ligands, which can serve as a catalyst for the reduction of N2 to NH3 and N2H4. Low-temperature protonation and reduction of the dinitrogen complex afforded the first structurally characterized neutral metal hydrazido(2-) species ([V]═NNH2), which mediated 15N2 conversion to 15NH3, indicating that it is a plausible intermediate of the catalysis. DFT calculations showed that the vanadium hydrazido complex [V]═NNH2 possessed a N-H bond dissociation free energy (BDFEN-H) of as high as 59.1 kcal/mol. The protonation of a vanadium amide complex ([V]-NH2) with [Ph2NH2][OTf] resulted in the release of NH3 and the formation of a vanadium triflate complex, which upon reduction under N2 afforded the vanadium dinitrogen complex. These transformations model the final steps of a vanadium-catalyzed N2 reduction cycle. Both experimental and theoretical studies suggest that the catalytic reaction may proceed via a distal pathway to liberate NH3. These findings provide unprecedented insights into the mechanism of N2 reduction related to FeV nitrogenase.

Scandium, titanium and vanadium complexes supported by PCP-type pincer ligands: synthesis, structure, and styrene polymerization activity.

A series of first-row early transition metal dialkyl complexes bearing pincer ligands [(POCOP)M(CH2SiMe3)2] (POCOP: (2,6-(tBu2PO)2-C6H3); 1-Sc: M = Sc; 1-Ti: M = Ti; 1-V: M = V) and [(PCP)M(CH2SiMe3)2] (PCP: (2,6-(tBu2PCH2)2-C6H3); 2-Sc: M = Sc; 2-Ti: M = Ti) have been synthesized. These dialkyl complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy, and solution magnetic susceptibility (Evans method) analyses appropriately. All the complexes exhibited square pyramidal geometries with different extents of distortion. The activities of these complexes were further explored in styrene polymerization, in which combinations of scandium complexes (1-Sc or 2-Sc) with [Ph3C][B(C6F5)4] were found to be active catalytic systems for highly syndiospecific (>99% rrrr) polymerization of styrene. Meanwhile, the Ti(III) complexes 1-Ti and 2-Ti showed rather low activity in styrene polymerization, which stands in sharp contrast to those in previous reports involving Ti(III) catalysts bearing cyclopentadienyl derivative ligands.