@article{HermannFantuzziArrowsmithetal.2020, author = {Hermann, Alexander and Fantuzzi, Felipe and Arrowsmith, Merle and Zorn, Theresa and Krummenacher, Ivo and Ritschel, Benedikt and Radacki, Krzysztof and Engels, Bernd and Braunschweig, Holger}, title = {Oxidation, Coordination, and Nickel-Mediated Deconstruction of a Highly Electron-Rich Diboron Analogue of 1,3,5-Hexatriene}, series = {Angewandte Chemie, International Edition}, volume = {59}, journal = {Angewandte Chemie, International Edition}, number = {36}, doi = {10.1002/anie.202006131}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-240652}, pages = {15717-15725}, year = {2020}, abstract = {The reductive coupling of an N-heterocyclic carbene (NHC) stabilized (dibromo)vinylborane yields a 1,2-divinyl- diborene, which, although isoelectronic to a 1,3,5-triene, displays no extended p conjugation because of twisting of the C\(_2\)B\(_2\)C\(_2\) chain. While this divinyldiborene coordinates to copper(I) and platinum(0) in an η\(^2\)-B\(_2\) and η\(^4\)-C\(_2\)B\(_2\) fashion, respectively, it undergoes a complex rearrangement to an η\(^4\)-1,3-diborete upon complexation with nickel(0).}, language = {en} } @article{GoettelGaoDotzaueretal.2020, author = {Goettel, James T. and Gao, Haopeng and Dotzauer, Simon and Braunschweig, Holger}, title = {\(^{Me}\)CAAC=N\(^{-}\): A Cyclic (Alkyl)(Amino)Carbene Imino Ligand}, series = {Chemistry - A European Journal}, volume = {26}, journal = {Chemistry - A European Journal}, number = {5}, doi = {10.1002/chem.201904715}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-212662}, pages = {1136-1143}, year = {2020}, abstract = {A cyclic (alkyl)(amino)carbene (CAAC) has been shown to react with a covalent azide similar to the Staudinger reaction. The reaction of \(^{Me}\)CAAC with trimethylsilyl azide afforded the N-silylated 2-iminopyrrolidine (\(^{Me}\)CAAC=NSiMe\(_{3}\)), which was fully characterized. This compound undergoes hydrolysis to afford the 2-iminopyrrolidine and trimethylsiloxane which co-crystallize as a hydrogen-bonded adduct. The N-silylated 2-iminopyrrolidine was used to transfer the novel pyrrolidine-2-iminato ligand onto both main-group and transition-metal centers. The reaction of the tetrabromodiborane bis(dimethyl sulfide) adduct with two equivalents of \(^{Me}\)CAAC=NSiMe\(_{3}\) afforded the disubstituted diborane. The reaction of \(^{Me}\)CAAC=NSiMe\(_{3}\) with TiCl\(_{4}\) and CpTiCl\(_{3}\) afforded \(^{Me}\)CAAC=NTiCl\(_{3}\) and \(^{Me}\)CAAC=NTiCl\(_{2}\)Cp, respectively.}, language = {en} }