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  - 
TY  - JOUR
A1  - Hagspiel, Stephan
A1  - Fantuzzi, Felipe
A1  - Dewhurst, Rian D.
A1  - Gärtner, Annalena
A1  - Lindl, Felix
A1  - Lamprecht, Anna
A1  - Braunschweig, Holger
T1  - Adducts of the parent boraphosphaketene H\(_2\)BPCO and their decarbonylative insertion chemistry
JF  - Angewandte Chemie International Edition
N2  - The first examples of Lewis base adducts of the parent boraphosphaketene (H\(_2\)B-PCO) and their cyclodimers are prepared. One of these adducts is shown to undergo mild decarbonylation and phosphinidene insertion into a B−C bond of a borole, forming very rare examples of 1,2-phosphaborinines, B/P isosteres of benzene. The strong donor properties of these 1,2-phosphaborinines are confirmed by the synthesis of their π complexes with the Group 6 metals.
KW  - inorganic chemistry
KW  - phosphorus
KW  - boron
KW  - decarbonylation
KW  - heterocycles
KW  - ketenes
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256470
VL  - 60
IS  - 24
ER  - 
TY  - JOUR
A1  - Hagspiel, Stephan
A1  - Fantuzzi, Felipe
A1  - Dewhurst, Rian D.
A1  - Gärtner, Annalena
A1  - Lindl, Felix
A1  - Lamprecht, Anna
A1  - Braunschweig, Holger
T1  - Addukte des Stammboraphosphaketens H\(_{2}\)BPCO und deren Insertionsreaktionen mittels Decarbonylierung
JF  - Angewandte Chemie
N2  - Die ersten Beispiele für Lewis-Basen-Addukte des Stammboraphosphaketens H\(_{2}\)B-PCO und ihre cyclischen Dimere wurden hergestellt. Eines dieser Addukte zeigt unter milden Bedingungen eine Decarbonylierung und anschließende Insertion des Phosphinidens in die B-C-Bindung eines Borols, was in der Bildung sehr seltener Beispiele für 1,2-Phosphaborinine, B,P-Isostere von Benzol, resultiert. Die starken Donoreigenschaften dieser 1,2-Phosphaborinine wurden durch die Synthese ihrer π-Komplexe mit Metallen der Gruppe 6 bestätigt.
KW  - Bor
KW  - Decarbonylierung
KW  - Heterocyclen
KW  - Ketene
KW  - Phosphor
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-244803
VL  - 133
IS  - 24
SP  - 13780
EP  - 13784
ER  - 
TY  - JOUR
A1  - Lu, Wei
A1  - Jayaraman, Arumugam
A1  - Fantuzzi, Felipe
A1  - Dewhurst, Rian D.
A1  - Härterich, Marcel
A1  - Dietz, Maximilian
A1  - Hagspiel, Stephan
A1  - Krummenbacher, Ivo
A1  - Hammond, Kai
A1  - Cui, Jingjing
A1  - Braunschweig, Holger
T1  - An unsymmetrical, cyclic diborene based on a chelating CAAC ligand and its small-molecule activation and rearrangement chemistry
JF  - Angewandte Chemie International Edition
N2  - A one-pot synthesis of a CAAC-stabilized, unsymmetrical, cyclic diborene was achieved via consecutive two-electron reduction steps from an adduct of CAAC and B\(_2\)Br\(_4\)(SMe\(_2\))\(_2\). Theoretical studies revealed that this diborene has a considerably smaller HOMO–LUMO gap than those of reported NHC- and phosphine-supported diborenes. Complexation of the diborene with [AuCl(PCy\(_3\))] afforded two diborene–Au\(^I\) π complexes, while reaction with DurBH\(_2\), P\(_4\) and a terminal acetylene led to the cleavage of B−H, P−P, and C−C π bonds, respectively. Thermal rearrangement of the diborene gave an electron-rich cyclic alkylideneborane, which readily coordinated to Ag\(^I\) via its B=C double bond.
KW  - inorganic chemistry
KW  - thermal rearrangement
KW  - alkylideneborane
KW  - carbene
KW  - diborene
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256576
VL  - 61
IS  - 3
ER  - 
TY  - JOUR
A1  - Brunecker, Carina
A1  - Müssig, Jonas H.
A1  - Arrowsmith, Merle
A1  - Fantuzzi, Felipe
A1  - Stoy, Andreas
A1  - Böhnke, Julian
A1  - Hofmann, Alexander
A1  - Bertermann, Rüdiger
A1  - Engels, Bernd
A1  - Braunschweig, Holger
T1  - Boranediyl‐ and Diborane(4)‐1,2‐diyl‐Bridged Platinum A‐Frame Complexes
JF  - Chemistry – A European Journal
N2  - Diplatinum A‐frame complexes with a bridging (di)boron unit in the apex position were synthesized in a single step by the double oxidative addition of dihalo(di)borane precursors at a bis(diphosphine)‐bridged Pt\(^{0}\)\(_{2}\) complex. While structurally analogous to well‐known μ‐borylene complexes, in which delocalized dative three‐center‐two‐electron M‐B‐M bonding prevails, theoretical investigations into the nature of Pt−B bonding in these A‐frame complexes show them to be rare dimetalla(di)boranes displaying two electron‐sharing Pt−B σ‐bonds. This is experimentally reflected in the low kinetic stability of these compounds, which are prone to loss of the (di)boron bridgehead unit.
KW  - boron
KW  - bonding
KW  - EDA-NOCV
KW  - oxidative addition
KW  - platinum
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-214707
VL  - 26
IS  - 39
SP  - 8518
EP  - 8523
ER  - 
TY  - JOUR
A1  - Saalfrank, Christian
A1  - Fantuzzi, Felipe
A1  - Kupfer, Thomas
A1  - Ritschel, Benedikt
A1  - Hammond, Kai
A1  - Krummenacher, Ivo
A1  - Bertermann, Rüdiger
A1  - Wirthensohn, Raphael
A1  - Finze, Maik
A1  - Schmid, Paul
A1  - Engel, Volker
A1  - Engels, Bernd
A1  - Braunschweig, Holger
T1  - cAAC‐stabilisierte 9,10‐Diboraanthracene – offenschalige Singulettbiradikale
JF  - Angewandte Chemie
N2  - Geringe HOMO-LUMO-Abstände und eine hohe Ladungsträgermobilität prädestinieren die höheren Acene für Anwendungen im Bereich der Organoelektronik. Die Leistungsfähigkeit derartiger Verbindungen steigt hierbei dramatisch mit der Anzahl anellierter Benzolringe. Größere Acenmengen sind synthetisch bisher jedoch nur für Acene bis Heptacen verlässlich zugänglich. Theoretischen Studien zufolge besitzen (Oligo)acene offenschalige Singulettbiradikal- und (Poly)acene polyradikalische Grundzustände. Eindeutige experimentelle Belege für diese Vorhersagen sind hingegen äußerst selten. Durch den Einbau von zwei Boratomen in das Anthracengrundgerüst konnten wir den HOMO-LUMO-Abstand von Acenen dramatisch verringern und zwar ohne die Notwendigkeit einer Ausweitung des konjugierten π-Systems. Stabilisierung der Borzentren durch cyclische (Alkyl)(amino)carbene lieferte hierbei neutrale 9,10-Diboraanthracene mit disjunkten, offenschaligen Singulettbiradikal-Grundzuständen.
KW  - Acene
KW  - Bindungsaktivierung
KW  - Biradikale
KW  - Bor
KW  - Heterocyclen
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-218582
VL  - 132
IS  - 43
SP  - 19502
EP  - 19507
ER  - 
TY  - JOUR
A1  - Saalfrank, Christian
A1  - Fantuzzi, Felipe
A1  - Kupfer, Thomas
A1  - Ritschel, Benedikt
A1  - Hammond, Kai
A1  - Krummenacher, Ivo
A1  - Bertermann, Rüdiger
A1  - Wirthensohn, Raphael
A1  - Finze, Maik
A1  - Schmid, Paul
A1  - Engel, Volker
A1  - Engels, Bernd
A1  - Braunschweig, Holger
T1  - cAAC‐Stabilized 9,10‐diboraanthracenes—Acenes with Open‐Shell Singlet Biradical Ground States
JF  - Angewandte Chemie International Edition
N2  - Narrow HOMO–LUMO gaps and high charge‐carrier mobilities make larger acenes potentially high‐efficient materials for organic electronic applications. The performance of such molecules was shown to significantly increase with increasing number of fused benzene rings. Bulk quantities, however, can only be obtained reliably for acenes up to heptacene. Theoretically, (oligo)acenes and (poly)acenes are predicted to have open‐shell singlet biradical and polyradical ground states, respectively, for which experimental evidence is still scarce. We have now been able to dramatically lower the HOMO–LUMO gap of acenes without the necessity of unfavorable elongation of their conjugated π system, by incorporating two boron atoms into the anthracene skeleton. Stabilizing the boron centers with cyclic (alkyl)(amino)carbenes gives neutral 9,10‐diboraanthracenes, which are shown to feature disjointed, open‐shell singlet biradical ground states.
KW  - acenes
KW  - biradicals
KW  - bond Activation
KW  - boron
KW  - heterocycles
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-217795
VL  - 59
IS  - 43
SP  - 19338
EP  - 19343
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  - Cui, Jingjing
A1  - Dietz, Maximilian
A1  - Härterich, Marcel
A1  - Fantuzzi, Felipe
A1  - Lu, Wei
A1  - Dewhurst, Rian D.
A1  - Braunschweig, Holger
T1  - Diphosphino-Functionalized 1,8-Naphthyridines: a Multifaceted Ligand Platform for Boranes and Diboranes
JF  - Chemistry—A European Journal
N2  - A 1,8-naphthyridine diphosphine (NDP) reacts with boron-containing Lewis acids to generate complexes featuring a number of different naphthyridine bonding modes. When exposed to diborane B\(_{2}\)Br\(_{4}\), NDP underwent self-deprotonation to afford [NDP-B\(_{2}\)Br\(_{3}\)]Br, an unsymmetrical diborane comprised of four fused rings. The reaction of two equivalents of monoborane BBr\(_{3}\) and NDP in a non-polar solvent provided the simple phosphine-borane adduct [NDP(BBr\(_{3}\))\(_{2}\)], which then underwent intramolecular halide abstraction to furnish the salt [NDP-BBr\(_{2}\)][BBr\(_{4}\)], featuring a different coordination mode from that of [NDP-B\(_{2}\)Br\(_{3}\)]Br. Direct deprotonation of NDP by KHMDS or PhCH2K generates mono- and dipotassium reagents, respectively. The monopotassium reagent reacts with one or half an equivalent of B\(_{2}\)(NMe\(_{2}\))\(_{2}\)Cl\(_{2}\) to afford NDP-based diboranes with three or four amino substituents.
KW  - pincer ligand
KW  - potassium reagent
KW  - diborane
KW  - naphthyridine
KW  - boron
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256994
VL  - 27
IS  - 63
ER  - 
TY  - JOUR
A1  - Hagspiel, Stephan
A1  - Arrowsmith, Merle
A1  - Fantuzzi, Felipe
A1  - Vargas, Alfredo
A1  - Rempel, Anna
A1  - Hermann, Alexander
A1  - Brückner, Tobias
A1  - Braunschweig, Holger
T1  - Highly colored boron-doped thiazolothiazoles from the reductive dimerization of boron isothiocyanates
JF  - Angewandte Chemie International Edition
N2  - Reduction of (CAAC)BBr\(_2\)(NCS) (CAAC=cyclic alkyl(amino)carbene) in the presence of a Lewis base L yields tricoordinate (CAAC)LB(NCS) borylenes which undergo reversible E/Z-isomerization. The same reduction in the absence of L yields deep blue, bis(CAAC)-stabilized, boron-doped, aromatic thiazolothiazoles resulting from the dimerization of dicoordinate (CAAC)B(NCS) borylene intermediates.
KW  - inorganic chemistry
KW  - aromaticity
KW  - reduction
KW  - fused thiazaboroles
KW  - DFT
KW  - borylenes
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256432
VL  - 60
IS  - 12
ER  - 
TY  - JOUR
A1  - Roy, Dipak Kumar
A1  - Tröster, Tobias
A1  - Fantuzzi, Felipe
A1  - Dewhurst, Rian D.
A1  - Lenczyk, Carsten
A1  - Radacki, Krzysztof
A1  - Pranckevicius, Conor
A1  - Engels, Bernd
A1  - Braunschweig, Holger
T1  - Isolation and Reactivity of an Antiaromatic s‐Block Metal Compound
JF  - Angewandte Chemie International Edition
N2  - The concepts of aromaticity and antiaromaticity have a long history, and countless demonstrations of these phenomena have been made with molecules based on elements from the p, d, and f blocks of the periodic table. In contrast, the limited oxidation‐state flexibility of the s‐block metals has long stood in the way of their participation in sophisticated π‐bonding arrangements, and truly antiaromatic systems containing s‐block metals are altogether absent or remain poorly defined. Using spectroscopic, structural, and computational techniques, we present herein the synthesis and authentication of a heterocyclic compound containing the alkaline earth metal beryllium that exhibits significant antiaromaticity, and detail its chemical reduction and Lewis‐base‐coordination chemistry.
KW  - antiaromaticity
KW  - aromaticity
KW  - beryllium
KW  - heterocycles
KW  - s-block metals
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-224447
VL  - 60
IS  - 7
SP  - 3812
EP  - 3819
ER  - 
TY  - JOUR
A1  - Brückner, Tobias
A1  - Fantuzzi, Felipe
A1  - Stennett, Tom E.
A1  - Krummenacher, Ivo
A1  - Dewhurst, Rian D.
A1  - Engels, Bernd
A1  - Braunschweig, Holger
T1  - Isolation of neutral, mono-, and dicationic B\(_2\)P\(_2\) rings by diphosphorus addition to a boron-boron triple bond
JF  - Angewandte Chemie International Edition
N2  - 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.
KW  - inorganic chemistry
KW  - radicals
KW  - boron
KW  - density functional calculations
KW  - oxidation
KW  - phosphorus heterocycles
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256451
VL  - 60
IS  - 24
ER  - 
TY  - JOUR
A1  - Brückner, Tobias
A1  - Ritschel, Benedikt
A1  - Jiménez‐Halla, J. Oscar C.
A1  - Fantuzzi, Felipe
A1  - Duwe, Dario
A1  - Markl, Christian
A1  - Dewhurst, Rian D.
A1  - Dietz, Maximilian
A1  - Braunschweig, Holger
T1  - Metal‐Free Intermolecular C−H Borylation of N‐Heterocycles at B−B Multiple Bonds
JF  - Angewandte Chemie International Edition
N2  - Carbene‐stabilized diborynes of the form LBBL (L=N‐heterocyclic carbene (NHC) or cyclic alkyl(amino)carbene (CAAC)) induce rapid, high yielding, intermolecular ortho‐C−H borylation at N‐heterocycles at room temperature. A simple pyridyldiborene is formed when an NHC‐stabilized diboryne is combined with pyridine, while a CAAC‐stabilized diboryne leads to activation of two pyridine molecules to give a tricyclic alkylideneborane, which can be forced to undergo a further H‐shift resulting in a zwitterionic, doubly benzo‐fused 1,3,2,5‐diazadiborinine by heating. Use of the extended N‐heteroaromatic quinoline leads to a borylmethyleneborane under mild conditions via an unprecedented boron‐carbon exchange process.
KW  - Boron
KW  - Borylation
KW  - Carbene
KW  - Diboryne
KW  - Hydroarylation
Y1  - 2023
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-312385
VL  - 62
IS  - 5
ER  - 
TY  - JOUR
A1  - Hermann, Alexander
A1  - Fantuzzi, Felipe
A1  - Arrowsmith, Merle
A1  - Zorn, Theresa
A1  - Krummenacher, Ivo
A1  - Ritschel, Benedikt
A1  - Radacki, Krzysztof
A1  - Engels, Bernd
A1  - Braunschweig, Holger
T1  - Oxidation, Coordination, and Nickel-Mediated Deconstruction of a Highly Electron-Rich Diboron Analogue of 1,3,5-Hexatriene
JF  - Angewandte Chemie, International Edition
N2  - 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).
KW  - boron
KW  - diborenes
KW  - carbenes
KW  - conjugation
KW  - density-functional calculations
KW  - rearrangements
KW  - structure elucidation
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-240652
VL  - 59
IS  - 36
ER  - 
TY  - JOUR
A1  - Brunecker, Carina
A1  - Arrowsmith, Merle
A1  - Fantuzzi, Felipe
A1  - Braunschweig, Holger
T1  - Platin‐vermittelte Kupplung von B=N‐Einheiten: Synthese von BNBN‐Analoga von 1,3‐Dienen und Butatrien
JF  - Angewandte Chemie
N2  - Die 1:2-Reaktion von [μ-(dmpm)Pt(nbe)]\(_{2}\) (dmpm=Bis(dimethylphosphino)methan, nbe=Norbornen) mit Cl\(_{2}\)BNR(SiMe\(_{3}\)) (R=tBu, SiMe\(_{3}\)) führt durch eine B-N-Kupplung über eine ClSiMe\(_{3}\)-Eliminierung zu unsymmetrischen (N-Aminoboryl)aminoboryl-Pt\(^{I}\)\(_{2}\)-Komplexen. Eine anschließende intramolekulare ClSiMe\(_{3}\)-Eliminierung des tBu-Derivats führt zu einer Cyclisierung der BNBN-Einheit unter Bildung eines einzigartigen 1,3,2,4-Diazadiboretidin-2-yl-Liganden. Im Gegensatz hierzu steht die analoge Reaktion mit Br\(_{2}\)BN(SiMe\(_{3}\))\(_{2}\), die über eine zweifache BrSiMe\(_{3}\)-Eliminierung zu einem Pt\(^{II}\)\(_{2}\)-A-Frame-Komplex führt, der von einem linearen Isoster des Butatriens verbrückt wird. Strukturelle und theoretische Daten bestätigen eine π-Elektronen-Delokalisierung über die gesamte BNBN-Einheit.
KW  - 1,3,2,4-Diazadiboretidin-2-yl-Ligand
KW  - A-Frame-Komplex
KW  - B-N-Kupplung
KW  - Butatrien-Analogon
KW  - Isosterie
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-244792
VL  - 133
IS  - 31
SP  - 17000
EP  - 17004
ER  - 
TY  - JOUR
A1  - Rang, Maximilian
A1  - Fantuzzi, Felipe
A1  - Arrowsmith, Merle
A1  - Krummenacher, Ivo
A1  - Beck, Eva
A1  - Witte, Robert
A1  - Matler, Alexander
A1  - Rempel, Anna
A1  - Bischof, Tobias
A1  - Radacki, Krzysztof
A1  - Engels, Bernd
A1  - Braunschweig, Holger
T1  - Reduktion und Umlagerung eines Bor(I)‐Carbonylkomplexes
JF  - Angewandte Chemie
N2  - Bei der Einelektronenreduktion eines durch eine cyclisches (Alkyl)(amino)carben (CAAC) stabilisierten Arylborylen-Carbonylkomplexes erfolgt die Bildung eines dimeren Borylketyl-Radikalanions, bedingt durch eine intramolekulare Arylmigration zum CO Kohlenstoffatom. Computergestützte Analyse liefert Hinweise auf eine radikalanionische [(CAAC)B(CO)Ar]\(^{.-}\) Zwischenstufe. Weiterführende Reduktion des entstandenen Komplexes liefert ein hoch nukleophiles (Boranyliden)methanolat.
KW  - Biradikale
KW  - Bor-Carbonylkomplexe
KW  - Dichtefunktionalrechnungen
KW  - Reduktionen
KW  - Umlagerungen
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-224409
VL  - 133
IS  - 6
SP  - 3000
EP  - 3005
ER  - 
TY  - JOUR
A1  - Weiser, Jonas
A1  - Cui, Jingjing
A1  - Dewhurst, Rian D.
A1  - Braunschweig, Holger
A1  - Engels, Bernd
A1  - Fantuzzi, Felipe
T1  - Structure and bonding of proximity‐enforced main‐group dimers stabilized by a rigid naphthyridine diimine ligand
JF  - Journal of Computational Chemistry
N2  - The development of ligands capable of effectively stabilizing highly reactive main‐group species has led to the experimental realization of a variety of systems with fascinating properties. In this work, we computationally investigate the electronic, structural, energetic, and bonding features of proximity‐enforced group 13–15 homodimers stabilized by a rigid expanded pincer ligand based on the 1,8‐naphthyridine (napy) core. We show that the redox‐active naphthyridine diimine (NDI) ligand enables a wide variety of structural motifs and element‐element interaction modes, the latter ranging from isolated, element‐centered lone pairs (e.g., E = Si, Ge) to cases where through‐space π bonds (E = Pb), element‐element multiple bonds (E = P, As) and biradical ground states (E = N) are observed. Our results hint at the feasibility of NDI‐E2 species as viable synthetic targets, highlighting the versatility and potential applications of napy‐based ligands in main‐group chemistry.
KW  - bond theory
KW  - computational chemistry
KW  - density functional calculations
KW  - main group elements
KW  - N ligands
Y1  - 2023
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-312586
VL  - 44
IS  - 3
SP  - 456
EP  - 467
ER  - 
TY  - JOUR
A1  - Franzsico, Marcos A. S.
A1  - Fantuzzi, Felipe
A1  - Cardozo, Thiago M.
A1  - Esteves, Pierre M.
A1  - Engels, Bernd
A1  - Oliveira, Ricardo R.
T1  - Taming the Antiferromagnetic Beast: Computational Design of Ultrashort Mn-Mn Bonds Stabilized by N-Heterocyclic Carbenes
JF  - Chemistry—A European Journal
N2  - The development of complexes featuring low-valent, multiply bonded metal centers is an exciting field with several potential applications. In this work, we describe the design principles and extensive computational investigation of new organometallic platforms featuring the elusive manganese-manganese bond stabilized by experimentally realized N-heterocyclic carbenes (NHCs). By using DFT computations benchmarked against multireference calculations, as well as MO- and VB-based bonding analyses, we could disentangle the various electronic and structural effects contributing to the thermodynamic and kinetic stability, as well as the experimental feasibility, of the systems. In particular, we explored the nature of the metal-carbene interaction and the role of the ancillary η\(^{6}\) coordination to the generation of Mn\(_{2}\) systems featuring ultrashort metal-metal bonds, closed-shell singlet multiplicities, and positive adiabatic singlet-triplet gaps. Our analysis identifies two distinct classes of viable synthetic targets, whose electrostructural properties are thoroughly investigated.
KW  - metal-metal interactions
KW  - ab initio calculations
KW  - carbene ligands
KW  - density functional calculations
KW  - manganese
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256874
VL  - 27
IS  - 47
ER  - 
TY  - JOUR
A1  - Ramler, Jaqueline
A1  - Fantuzzi, Felipe
A1  - Geist, Felix
A1  - Hanft, Anna
A1  - Braunschweig, Holger
A1  - Engels, Bernd
A1  - Lichtenberg, Crispin
T1  - The dimethylbismuth cation: entry into dative Bi-Bi bonding and unconventional methyl exchange
JF  - Angewandte Chemie International Edition
N2  - The dimethyl bismuth cation, [BiMe\(_2\)(SbF\(_6\))], has been isolated and characterized. Reaction with BiMe\(_3\) allows access to the first compound featuring Bi→Bi donor–acceptor bonding. In solution, dynamic behavior with methyl exchange via an unusual S\(_E\)2 mechanism is observed, underlining the unique properties of bismuth species as soft Lewis acids with the ability to undergo reversible Bi−C bond cleavage.
KW  - inorganic chemistry
KW  - methyl exchange
KW  - bismuth
KW  - cationic species
KW  - electrophilic substitution
KW  - Lewis acidity
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256543
VL  - 60
ER  - 
TY  - INPR
A1  - Schmidt, Uwe
A1  - Fantuzzi, Felipe
A1  - Arrowsmith, Merle
A1  - Hermann, Alexander
A1  - Prieschl, Dominic
A1  - Rempel, Anna
A1  - Engels, Bernd
A1  - Braunschweig, Holger
T1  - Tuneable reduction of cymantrenylboranes to diborenes or borylene-derived boratafulvenes
T2  - Chemical Communications
N2  - Whereas the reduction of N-heterocyclic carbene (NHC)-stabilised cymantrenyldibromoboranes, (NHC)BBr\(_2\)Cym, in benzene results in formation of the corresponding diborenes (NHC)\(_2\)B\(_2\)Cym\(_2\), a change of solvent to THF yields a borylene of the form (NHC)\(_2\)BCym, stabilised through its boratafulvene resonance form.
KW  - Borylene
KW  - Diborene
KW  - Boranes
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-222149
ER  -