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A cyclic alkyl(amino)carbene (CAAC)-stabilized dicoordinate aminoborylene is synthesized by the twofold reduction of a [(CAAC)BCl2 (TMP)] (TMP=2,6-tetramethylpiperidyl) precursor. NMR-spectroscopic, X-ray crystallographic and computational analyses confirm the cumulenic nature of the central C=B=N moiety. Irradiation of [(CAAC)B(TMP)] (2) resulted in an intramolecular C-C bond activation, leading to a doubly-fused C10 BN heterocycle, while the reaction with acetonitrile resulted in an aryl migration from the CAAC to the acetonitrile nitrogen atom, concomitant with tautomerization of the latter to a boron-bound allylamino ligand. One-electron oxidation of 2 with CuX (X=Cl, Br) afforded the corresponding amino(halo)boryl radicals, which were characterized by EPR spectroscopy and DFT calculations. Placing 2 under an atmosphere of CO afforded the tricoordinate (CAAC,CO)-stabilized aminoborylene. Finally, the twofold oxidation of 2 with chalcogens led, in the case of N2O and sulfur, to the splitting of the B-CCAAC bond and formation of the 2,4-diamino-1,3,2,4-dichalcogenadiboretanes and CAAC-chalcogen adducts, whereas with selenium a monomeric boraselenone was isolated, which showed some degree of B-Se multiple bonding. [ABSTRACT FROM AUTHOR]

A number of novel alkynyl‐functionalized diarylbis(dimethylamino)diboranes(4) are prepared by salt metathesis, and the appended alkynyl groups are subjected to hydroboration. Their reactions with monohydroboranes lead to discrete boryl‐appended diborane(4) species, while dihydroboranes induce their catenation to oligomeric species, the first known examples of well‐characterized macromolecular species with B−B bonds. The oligomeric species were found to comprise up to ten repeat units and are soluble in common organic solvents. Some of the oligomeric species have good air stability and all were characterized by NMR and vibrational spectroscopy and size‐exclusion chromatography techniques. [ABSTRACT FROM AUTHOR]

The reactions of terminal acetylenes with doubly Lewis base-stabilised diborenes resulted in different outcomes depending on the nature of the ligands at boron and the conformation of the diborene (cyclic versus acyclic). N-heterocyclic carbene (NHC)-stabilised diborenes tended to undergo anti -selective hydroalkynylation at room temperature, whereas [2 + 2] cycloaddition was observed at higher temperatures, invariably followed by a C-N bond activation at one NHC ligand, leading to the ring-expansion of the initially formed BCBC ring and formation of novel boron-containing heterocycles. For phosphine-stabilised diborenes only [2 + 2] cycloaddition was observed, followed by a rearrangement of the resulting 1,2-dihydro-1,2-diborete to the corresponding 1,3-isomer, which amounts to complete scission of both the B[double bond, length as m-dash]B double and C[triple bond, length as m-dash]C triple bonds of the reactants. The elusive 1,2-isomer was finally trapped by using a cyclic phosphine-stabilised diborene, which prevented rearrangement to the 1,3-isomer. Extensive density functional theory (DFT) calculations provide a rationale for the selectivity observed., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)