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Article Dans Une Revue Chemical Science Année : 2023

An orbitally adapted push-pull template for N2 activation and reduction to diazene-diide

Résumé

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). Those compounds feature only one N-B linkage of 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 by 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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Dates et versions

hal-04299114 , version 1 (22-11-2023)

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Paternité

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David Specklin, Marie-Christine Boegli, Anaïs Coffinet, Léon Escomel, Laure Vendier, et al.. An orbitally adapted push-pull template for N2 activation and reduction to diazene-diide. Chemical Science, 2023, 14 (48), pp.14262-14270. ⟨10.1039/d3sc04390h⟩. ⟨hal-04299114⟩
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