Molecular chains of two-coordinate carbon atoms (cumulenes) have long been targeted, due to interest in the electronic structure and applications of extended π-systems, and their relationship to the carbon allotrope, carbyne. While formal (isoelectronic) B═N for C═C substitution has been employed in two-dimensional (2-D) materials, unsaturated one-dimensional all-inorganic "molecular wires" are unknown. Here, we report high-yielding synthetic approaches to heterocumulenes containing a five-atom BNBNB chain, the geometric structure of which can be modified by choice of end group. The diamido-capped system is bent at the 2-/4-positions, and natural resonance theory calculations reveal significant contributions from B═N(:)-B≡N-B resonance forms featuring a lone pair at N (consistent with observed N-centered nucleophilicity). Molecular modification to generate a linear system best described by a B═N═B═N═B resonance structure involves chemical transformation of the capping groups (using B(C5F5)3) to enhance their π-acidity and conjugate the N-lone pairs.
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