TY  - JOUR
A1  - Gerlach, Marius
A1  - Monninger, Sophie
A1  - Schleier, Domenik
A1  - Hemberger, Patrick
A1  - Goettel, James T.
A1  - Braunschweig, Holger
A1  - Fischer, Ingo
T1  - Photoelectron Photoion Coincidence Spectroscopy of NCl\(_{3}\) and NCl\(_{2}\)
JF  - ChemPhysChem
N2  - We investigate NCl\(_{3}\) and the NCl\(_{2}\) radical by photoelectron-photoion coincidence spectroscopy using synchrotron radiation. The mass selected threshold photoelectron spectrum (ms-TPES) of NCl\(_{3}\) is broad and unstructured due to the large geometry change. An ionization energy of 9.7±0.1 eV is estimated from the spectrum and supported by computations. NCl2 is generated by photolysis at 213 nm from NCl\(_{3}\) and its ms-TPES shows an extended vibrational progression with a 90 meV spacing that is assigned to the symmetric N−Cl stretching mode in the cation. An adiabatic ionization energy of 9.94 ± 0.02 eV is determined.
KW  - radicals
KW  - photoelectron spectroscopy
KW  - synchrotron radiation
KW  - nitrogen trichloride
KW  - photolysis
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-257322
VL  - 22
IS  - 21
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  - 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  - 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  - 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  - Muessig, Jonas H.
A1  - Lisinetskaya, Polina
A1  - Dewhurst, Rian D.
A1  - Bertermann, Rüdiger
A1  - Thaler, Melanie
A1  - Mitric, Roland
A1  - Braunschweig, Holger
T1  - Tetraiododiborane(4) (B\(_2\)I\(_4\)) is a Polymer based on sp\(^3\) Boron in the Solid State
JF  - Angewandte Chemie International Edition
N2  - Herein we present the first solid‐state structures of tetraiododiborane(4) (B\(_2\)I\(_4\)), which was long believed to exist in all phases as discrete molecules with planar, tricoordinate boron atoms, like the lighter tetrahalodiboranes(4) B\(_2\)F\(_4\), B\(_2\)Cl\(_4\), and B\(_2\)Br\(_4\). Single‐crystal X‐ray diffraction, solid‐state NMR, and IR measurements indicate that B\(_2\)I\(_4\) in fact exists as two different polymeric forms in the solid state, both of which feature boron atoms in tetrahedral environments. DFT calculations are used to simulate the IR spectra of the solution and solid‐state structures, and these are compared with the experimental spectra.
KW  - boron tetraiodide
KW  - boron
KW  - density functional theory
KW  - diborane
KW  - halides
KW  - solid-state sturcture
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-209428
VL  - 59
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  - Schmidt, Paul
A1  - Fantuzzi, Felipe
A1  - Klopf, Jonas
A1  - Schröder, Niklas B.
A1  - Dewhurst, Rian D.
A1  - Braunschweig, Holger
A1  - Engel, Volker
A1  - Engels, Bernd
T1  - Twisting versus delocalization in CAAC- and NHC-stabilized boron-based biradicals: the roles of sterics and electronics
JF  - Chemistry - A European Journal
N2  - Twisted boron-based biradicals featuring unsaturated C\(_2\)R\(_2\) (R=Et, Me) bridges and stabilization by cyclic (alkyl)(amino)carbenes (CAACs) were recently prepared. These species show remarkable geometrical and electronic differences with respect to their unbridged counterparts. Herein, a thorough computational investigation on the origin of their distinct electrostructural properties is performed. It is shown that steric effects are mostly responsible for the preference for twisted over planar structures. The ground-state multiplicity of the twisted structure is modulated by the σ framework of the bridge, and different R groups lead to distinct multiplicities. In line with the experimental data, a planar structure driven by delocalization effects is observed as global minimum for R=H. The synthetic elusiveness of C\(_2\)R\(_2\)-bridged systems featuring N-heterocyclic carbenes (NHCs) was also investigated. These results could contribute to the engineering of novel main group biradicals.
KW  - chemistry
KW  - radicals
KW  - ab initio calculations
KW  - boron
KW  - carbene ligands
KW  - density functional calculations
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256636
VL  - 27
IS  - 16
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  -