@unpublished{BraunschweigKrummenacherLichtenbergetal.2016, author = {Braunschweig, Holger and Krummenacher, Ivo and Lichtenberg, Crispin and Mattock, James and Sch{\"a}fer, Marius and Schmidt, Uwe and Schneider, Christoph and Steffenhagen, Thomas and Ullrich, Stefan and Vargas, Alfredo}, title = {Dibora[2]ferrocenophane: A Carbene-Stabilized Diborene in a Strained cis-Configuration}, series = {Angewandte Chemie, International Edition}, journal = {Angewandte Chemie, International Edition}, doi = {10.1002/anie.201609601}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-141981}, pages = {9}, year = {2016}, abstract = {Unsaturated bridges that link the two cyclopentadienyl ligands together in strained ansa metallocenes are rare and limited to carbon-carbon double bonds. The synthesis and isolation of a strained ferrocenophane containing an unsaturated two-boron bridge, isoelectronic with a C=C double bond, was achieved by reduction of a carbene-stabilized 1,1'-bis(dihaloboryl)ferrocene. A combination of spectroscopic and electrochemical measurements as well as density functional theory (DFT) calculations was used to assess the influence of the unprecedented strained cis configuration on the optical and electrochemical properties of the carbene-stabilized diborene unit. Initial reactivity studies show that the dibora[2]ferrocenophane is prone to boron-boron double bond cleavage reactions.}, subject = {Metallocene}, language = {en} } @article{BruecknerFantuzziStennettetal.2021, author = {Br{\"u}ckner, Tobias and Fantuzzi, Felipe and Stennett, Tom E. and Krummenacher, Ivo and Dewhurst, Rian D. and Engels, Bernd and Braunschweig, Holger}, title = {Isolation of neutral, mono-, and dicationic B\(_2\)P\(_2\) rings by diphosphorus addition to a boron-boron triple bond}, series = {Angewandte Chemie International Edition}, volume = {60}, journal = {Angewandte Chemie International Edition}, number = {24}, doi = {10.1002/anie.202102218}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256451}, pages = {13661-13665}, year = {2021}, abstract = {The NHC-stabilised diboryne (B\(_2\)(SIDep)\(_2\); SIDep=1,3-bis(2,6-diethylphenyl)imidazolin-2-ylidene) undergoes a high-yielding P-P bond activation with tetraethyldiphosphine at room temperature to form a B\(_2\)P\(_2\) heterocycle via a diphosphoryldiborene by 1,2-diphosphination. The heterocycle can be oxidised to a radical cation and a dication, respectively, depending on the oxidant used and its counterion. Starting from the planar, neutral 1,3-bis(alkylidene)-1,3-diborata-2,4-diphosphoniocyclobutane, each oxidation step leads to decreased B-B distances and loss of planarity by cationisation. X-ray analyses in conjunction with DFT and CASSCF/NEVPT2 calculations reveal closed-shell singlet, butterfly-shaped structures for the NHC-stabilised dicationic B\(_2\)P\(_2\) rings, with their diradicaloid, planar-ring isomers lying close in energy.}, language = {en} }