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A molybdenum–nitride complex bearing a pyridine-based PNP-type pincer ligand derived from dinitrogen is reacted with various kinds of carbon-centered electrophiles to functionalize the nitride ligand in the molybdenum complex. Methylation with MeOTf and acylation with diphenylacetyl chloride of the nitride complex afford the corresponding imide complexes via a carbon–nitrogen bond formation. In the case of reactions with phenylisocyanate and diphenylketene, the PNP ligand works as a non-innocent ligand to form the corresponding ureate and acylimide complexes, respectively. These newly synthesized complexes are characterized by X-ray analysis. As a further transformation of the prepared imide complexes, hydrolysis of the molybdenum–acylimide complex proceeds to give the corresponding amide as an organonitrogen compound together with the corresponding molybdenum–oxo complex. This result indicates that the nitrogen molecule is converted into organic amide mediated by the molybdenum–nitride complex. [ABSTRACT FROM AUTHOR]

Molybdenum complexes bearing an anionic pyrrole-based PNP-type pincer ligand have been prepared and have been found to work as catalysts for the conversion of N2 into NH3 under ambient conditions. [ABSTRACT FROM AUTHOR]

Rhodium complexes bearing an anionic pyrrole-based PNP-type pincer ligand are synthesised and found to work as effective catalysts for the transformation of molecular dinitrogen into tris(trimethylsilyl)amine under mild reaction conditions. This is the first successful example of rhodium-catalysed dinitrogen reduction under mild reaction conditions. [ABSTRACT FROM AUTHOR]

Iron–chloride, –dinitrogen, and –methyl complexes bearing anionic carbazole-based PNP-type pincer ligands are designed, prepared and characterized by X-ray analysis. Some iron complexes are found to work as catalysts toward nitrogen fixation under mild reaction conditions. [ABSTRACT FROM AUTHOR]

Iron–dinitrogen complexes bearing methyl- and phenyl-substituted pyrrole-based anionic PNP-type pincer ligands are prepared and characterized by X-ray analysis. The former complex is found to work as a more effective catalyst than that bearing a non-substituted PNP-type pincer ligand toward the transformation of nitrogen gas into ammonia and hydrazine under mild reaction conditions. [ABSTRACT FROM AUTHOR]

A dinitrogen-bridged dimolybdenum-tetrachloride complex is prepared and reduced with Super-Hydride (LiBHEt3) to afford the corresponding dimolybdenum-dinitrogen complex together with the formation of molecular dihydrogen. This reaction proceeds via the ligand exchange of the coordinated dihydrogen generated in situ with molecular dinitrogen. [ABSTRACT FROM AUTHOR]

Novel mono- and dimolybdenum–dinitrogen complexes bearing an arsenic-containing ANA-type pincer ligand are prepared and characterized by X-ray analyses. These complexes afford a stoichiometric amount of ammonia by treatment with sulfuric acid at room temperature. [ABSTRACT FROM AUTHOR]

A molybdenum-nitride complex bearing a pyridine-based PNP-type pincer ligand derived from dinitrogen is reacted with various kinds of carbon-centered electrophiles to functionalize the nitride ligand in the molybdenum complex. Methylation with MeOTf and acylation with diphenylacetyl chloride of the nitride complex afford the corresponding imide complexes via a carbon-nitrogen bond formation. In the case of reactions with phenylisocyanate and diphenylketene, the PNP ligand works as a non-innocent ligand to form the corresponding ureate and acylimide complexes, respectively. These newly synthesized complexes are characterized by X-ray analysis. As a further transformation of the prepared imide complexes, hydrolysis of the molybdenum-acylimide complex proceeds to give the corresponding amide as an organonitrogen compound together with the corresponding molybdenum-oxo complex. This result indicates that the nitrogen molecule is converted into organic amide mediated by the molybdenum-nitride complex.