Recent years have witnessed a significant development in the area of complexes with boron-centered ligands with respect to new and unusual coordination modes. [1] Selected examples include heterodinuclear 1  [2] and semi-briding borylenes 2  [3] as well as neutral 3  , cationic 4  or anionic 5  metalloborylenes and metal-base adducts thereof 3a [4]. These findings emphasize the close relationship between borylenes and carbonyls as well as carbenes, which constitute ligand systems of pivotal importance in organometallic chemistry.Based on the gradual elucidation of the electronic structure of borylene complexes, specific reactivity patterns have started to emerge, in particular B�R transfer to transition metals [5] and unsaturated organic substrates [6] as well as metathesis reactions [7]. Thus, a variety of borylene-based functionalizations of organic and inorganic substrates will be presented, establishing borylenes as highly useful synthons in organic and inorganic transformations, which are not accessible by conventional organoboron chemistry.(1) H. Braunschweig, C. Kollann, D. Rais, Angew. Chem. Int. Ed. 2006  ,45, 5254.(2) H. Braunschweig, K. Radacki, D. Rais, F. Seeler, K. Uttinger, J. Am. Chem. Soc. 2005  , 127, 1386.(3) H. Braunschweig, D. Rais, K. Uttinger, Angew. Chem. Int. Ed. 2005  , 44, 3763.(4) H. Braunschweig, M. Burzler, R. D. Dewhurst, K. Radacki, Angew. Chem Int. Ed. 2008  , 47, 5650.(5) H. Braunschweig, M. Forster, T. Kupfer, F. Seeler, Angew. Chem Int. Ed. 2010  , 49, 9517.(6) H. Braunschweig, R. D. Dewhurst, T. Herbst, K. Radacki, Angew. Chem Int. Ed. 2008  , 47, 5978.(7) H. Braunschweig, M. Burzler, K. Radacki, F. Seeler, Angew. Chem Int. Ed. 2007  , 46, 8071.

Transfer, metathesis, and catenation: Reactivity patterns emerging from borylenecomplexes

247th National Meeting (2014)

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