TY  - JOUR
A1  - Matler, Alexander
A1  - Arrowsmith, Merle
A1  - Schorr, Fabian
A1  - Hermann, Alexander
A1  - Hofmann, Alexander
A1  - Lenczyk, Carsten
A1  - Braunschweig, Holger
T1  - Reactivity of Terminal Iron Borylenes and Bis(borylenes) with Carbodiimides: Cycloaddition, Metathesis, Insertion and C−H Activation Pathways
JF  - European Journal of Inorganic Chemistry
N2  - The reactions of carbodiimides with the iron arylborylene complex [Fe=BDur(CO)\(_{3}\)(PMe\(_{3}\))] (Dur=2,3,5,6-Me\(_{4}\)C\(_{6}\)H) and the iron bis(borylene) complex [Fe{=BDur}{=BN(SiMe\(_{3}\))\(_{2}\)}(CO)\(_{3}\)] yield a wide variety of temperature-dependent products, including known FeBNC and novel FeBNB metallacycles, complexes of N-heterocyclic boracarbene and spiro-boracarbene ligands and a unique 1,3,2,4-diazadiborolyl pianostool complex, characterized by NMR spectroscopy and X-ray crystallography. The product distributions can be rationalized by considering sequences of cycloaddition, metathesis, insertion, and C−H activation pathways mainly governed by sterics.
KW  - structure elucidation
KW  - borylene complexes
KW  - cycloaddition
KW  - metathesis
KW  - reaction mechanisms
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-257397
VL  - 2021
IS  - 45
ER  - 
TY  - JOUR
A1  - Witte, Robert
A1  - Arrowsmith, Merle
A1  - Lamprecht, Anna
A1  - Schorr, Fabian
A1  - Krummenacher, Ivo
A1  - Braunschweig, Holger
T1  - C−C and C−N Bond Activation, Lewis‐Base Coordination and One‐ and Two‐Electron Oxidation at a Linear Aminoborylene
JF  - Chemistry – A European Journal
N2  - A cyclic alkyl(amino)carbene (CAAC)‐stabilized dicoordinate aminoborylene is synthesized by the twofold reduction of a [(CAAC)BCl\(_{2}\)(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 C\(_{10}\)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 N\(_{2}\)O and sulfur, to the splitting of the B−C\(_{CAAC}\) 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.
KW  - bond activation
KW  - boraselenone
KW  - dicoordinate borylene
KW  - one-electron oxidation
KW  - push-pull stabilization
Y1  - 2023
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-312491
VL  - 29
IS  - 16
ER  - 
TY  - JOUR
A1  - Schorr, Fabian
A1  - Schopper, Nils
A1  - Riensch, Nicolas
A1  - Fantuzzi, Felipe
A1  - Neder, Marco
A1  - Dewhurst, Rian D.
A1  - Thiess, Thorsten
A1  - Brückner, Tobias
A1  - Hammond, Kai
A1  - Helten, Holger
A1  - Finze, Maik
A1  - Braunschweig, Holger
T1  - Controlled Synthesis of Oligomers Containing Main-Chain B(sp\(^{2}\))-B(sp\(^{2}\)) Bonds
JF  - Chemistry—A European Journal
N2  - 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.
KW  - oligomerization
KW  - boron
KW  - catenation
KW  - diborane
KW  - hydroboration
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-257274
VL  - 27
IS  - 64
ER  - 
TY  - JOUR
A1  - Czernetzki, Corinna
A1  - Arrowsmith, Merle
A1  - Fantuzzi, Felipe
A1  - Gärtner, Annalena
A1  - Tröster, Tobias
A1  - Krummenacher, Ivo
A1  - Schorr, Fabian
A1  - Braunschweig, Holger
T1  - A neutral beryllium(I) radical
JF  - Angewandte Chemie International Edition
N2  - The reduction of a cyclic alkyl(amino)carbene (CAAC)-stabilized organoberyllium chloride yields the first neutral beryllium radical, which was characterized by EPR, IR, UV/Vis spectroscopy and X-ray crystallography. DFT calculations show significant spin density at beryllium and confirm donor–acceptor bonding between an alkylberyllium radical fragment and a neutral CAAC ligand.
KW  - inorganic chemistry
KW  - X-ray crystallography
KW  - Beryllium
KW  - cyclic alkyl(amino)carbene
KW  - EDA-NOCV
KW  - radical
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256529
VL  - 60
IS  - 38
ER  -