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Updated: Jul 8, 2025

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid
Published on: November 15, 2017
An orbitally adapted push-pull template for N2 activation and reduction to diazene-diide
David Specklin1, Marie-Christine Boegli1, Anaïs Coffinet1
1LCC-CNRS, Université de Toulouse, CNRS, UPS 205 route de Narbonne BP44099 F-31077 Toulouse Cedex 4 France antoine.simonneau@lcc-toulouse.fr.
Abstract:
A Lewis superacidic bis(borane) C6F4{B(C6F5)2}2 was reacted with tungsten N2-complexes [W(N2)2(R2PCH2CH2PR2)2] (R = Ph or Et), affording zwitterionic boryldiazenido W(ii) complexes trans-[W(L)(R2PCH2CH2PR2)2(N2{B(C6F5)2(C6F4B(C6F5)3})] (L = ø, N2 or THF). These compounds feature only one N-B linkage of the covalent type, as a result of intramolecular boron-to-boron C6F5 transfer. Complex trans-[W(THF)(Et2PCH2CH2PEt2)2(N2{B(C6F5)2C6F4B(C6F5)3})] (5) was shown to split H2, leading to a seven-coordinate complex [W(H)2(Et2PCH2CH2PEt2)2(N2{B(C6F5)2}2C6F4)] (7). Interestingly, hydride storage at the metal triggers backward C6F5 transfer. This reverts the bis(boron) moiety to its bis(borane) state, now doubly binding the distal N, with structural parameters and DFT computations pointing to dative N→B bonding. By comparison with an N2 complex [W(H)2(Et2PCH2CH2PEt2)2(N2{B(C6F5)3}] (10) differing only in the Lewis acid (LA), namely B(C6F5)3, coordinated to the distal N, we demonstrate that two-fold LA coordination imparts strong N2 activation up to the diazene-diide (N22-) state. To the best of our knowledge, this is the first example of a neutral LA coordination that induces reduction of N2.
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