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  - 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  - 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  -