The splitting of dinitrogen into molecular nitrides provides a potential, Haber-Bosch inspired entry into N2-functionalization. Surprisingly, tungsten mediated N2-splitting is rare despite the prevalence of Mo in this chemistry.1 Our previous results on tungsten N2-splitting showed a strong dependence of the respective acid cleaving the NN bond in [{(PNP)ClW}2-μ-N2], (1) (PNP- = N(CH2CH2PtBu2)2-) into terminal nitrides.2 In continuation of this work controlling N2-splitting reactivity with transition metal pincer platforms, we here report the reaction of 1 with CO. The dinuclear carbonyl complex [{(PNP)Cl(CO)W}2-μ-N2] (2) is isolated where the {W-NN-W} core is retained. The structural properties, reactivity, and redox chemistry of 2 are presented in comparison with 1 allowing for discussion of ligand effects on N2-functionalization. Reaction of 2 with different reducing agents and acids were explored to activate N2. An alternative route to synthesize a tungsten nitride from a low valent tungsten carbonyl complex is also discussed.

Exploring N2 activation of [{(PNP)Cl(CO)W}2-μ-N2] with reducing agents and Brønsted acids

256th National Meeting (2018)

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