All-Inorganic sp-Chain Ligands: Isoelectronic B/N Analogues of E. O. Fischer's Alkynylcarbynes.

Borylation of a tungsten-bound N 2 ligand and halide abstraction provides access to a cationic complex with an unprecedented linear NNBR ligand. This complex undergoes [3+2] cycloaddition with azides, and an unexpected chain-extension reaction with an iminoborane, leading to a complex with a five-atom B/N chain. These two [NNBR]-containing complexes, inorganic analogues of E. O. Fischer's alkynylcarbynes, are very rare examples of molecules containing all-inorganic chains of sp-hybridized atoms.