4.8 Article

Diboriranide s-Complexes of d- and p-Block Metals

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202308678

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Aromatics; Boron; Coordination Chemistry; Transition Metals

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A straightforward synthesis of the first peraryl diboriranide was reported, demonstrating its preference for s-type coordination modes towards main group and transition metal centers. The synthesis involved the preparation of the non-classical diborirane from a readily available 1,2-dichlorodiborane(4) and subsequent conversion to the peraryl diboriranide lithium salt in three steps. Representative complexes with tin, copper, gold, and zinc were prepared and characterized to illustrate the reactivity and complexation behavior of the diboriranide.
Diboriranides are the smallest conceivable monoanionic aromatic cycles, yet only limited examples have been reported and their reactivity and complexation behavior remain completely unexplored. We report a straightforward synthesis of the first peraryl diboriranide c-(DurB)(2)CPh- as its lithium salt in three steps via the corresponding non-classical diborirane from a readily available 1,2-dichlorodiborane(4) (Dur=2,3,5,6-tetramethylphenyl). With the preparation and complete characterization of representative complexes with tin, copper, gold and zinc, we demonstrate the strong preference of the diboriranide for s-type coordination modes towards main group and transition metal centers under unperturbed retention of the three-membered B2C-ring's 2e- p-system.

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