@article{ArrowsmithEndresHeinzetal.2021, author = {Arrowsmith, Merle and Endres, Sara and Heinz, Myron and Nestler, Vincent and Holthausen, Max C. and Braunschweig, Holger}, title = {Probing the Boundaries between Lewis-Basic and Redox Behavior of a Parent Borylene}, series = {Chemistry—A European Journal}, volume = {27}, journal = {Chemistry—A European Journal}, number = {70}, doi = {10.1002/chem.202103256}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257154}, pages = {17660-17668}, year = {2021}, abstract = {The parent borylene (CAAC)(Me\(_{3}\)P)BH, 1 (CAAC=cyclic alkyl(amino)carbene), acts both as a Lewis base and one-electron reducing agent towards group 13 trichlorides (ECl\(_{3}\), E=B, Al, Ga, In), yielding the adducts 1-ECl\(_{3}\) and increasing proportions of the radical cation [1]\(^{•+}\) for the heavier group 13 analogues. With boron trihalides (BX\(_{3}\), X=F, Cl, Br, I) 1 undergoes sequential adduct formation and halide abstraction reactions to yield borylboronium cations and shows an increasing tendency towards redox processes for the heavier halides. Calculations confirm that 1 acts as a strong Lewis base towards EX3 and show a marked increase in the B-E bond dissociation energies down both group 13 and the halide group.}, language = {en} }