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  - Hock, Andreas
A1  - Werner, Luis
A1  - Riethmann, Melanie
A1  - Radius, Udo
T1  - Bis‐NHC Aluminium and Gallium Dihydride Cations [(NHC)\(_{2}\)EH\(_{2}\)]\(^{+}\) (E = Al, Ga)
JF  - European Journal of Inorganic Chemistry
N2  - The NHC alane and gallane adducts (NHC)·AlH\(_{2}\)I (NHC = Me\(_{2}\)Im\(^{Me}\) 7, iPr\(_{2}\)Im 8, iPr\(_{2}\)Im\(^{Me}\) 9) and (NHC)·GaH\(_{2}\)I (NHC = Me\(_{2}\)Im\(^{Me}\) 10, iPr\(_{2}\)Im\(^{Me}\) 11, Dipp\(_{2}\)Im 12; R\(_{2}\)Im = 1,3‐di‐organyl‐imidazolin‐2‐ylidene; Dipp = 2,6‐diisopropylphenyl; iPr = isopropyl; Me\(_{2}\)Im\(^{Me}\) = 1,3,4,5‐tetra‐methyl‐imidazolin‐2‐ylidene) were prepared either by the simple yet efficient reaction of the NHC adduct (NHC)·AlH\(_{3}\) with elemental iodine or by the treatment of (NHC)·GaH\(_{3}\) with an excess of methyl iodide at room temperature. The reaction of one equivalent of the group 13 NHC complexes with an additional equivalent of the corresponding NHC afforded cationic aluminium and gallium hydrides [(NHC)\(_{2}\)·AlH\(_{2}\)]\(^{+}\)I− (NHC = Me\(_{2}\)Im\(^{Me}\) 13, iPr\(_{2}\)Im 14, iPr\(_{2}\)Im\(^{Me}\) 15) and [(NHC)\(_{2}\)·GaH\(_{2}\)]\(^{+}\)I− (NHC = Me\(_{2}\)Im\(^{Me}\) 16, iPr\(_{2}\)Im\(^{Me}\) 17) and the normal and abnormal NHC coordinated compound [(Dipp\(_{2}\)Im)·GaH\(_{2}\)(aDipp\(_{2}\)Im)]+I− 18. Compounds 7–18 were isolated and characterized by means of elemental analysis, IR and multinuclear NMR spectroscopy and by X‐ray diffraction of the compounds 7, 9, 10, 15, 16 and 18.
KW  - aluminium
KW  - cations
KW  - Gallium
KW  - main group elements
KW  - heterocyclic carbenes
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-217928
VL  - 2020
IS  - 42
SP  - 4015
EP  - 4023
ER  - 
TY  - JOUR
A1  - Ewing, William C.
A1  - Dellermann, Theresa
A1  - Angel Wong, Y. T.
A1  - Mattock, James D.
A1  - Vargas, Alfredo
A1  - Bryce, David L.
A1  - Dewhurst, Rian D.
A1  - Braunschweig, Holger
T1  - \(\pi\)‐Complexes of Diborynes with Main Group Atoms
JF  - Chemistry – An Asian Journal
N2  - We present herein an in‐depth study of complexes in which a molecule containing a boron‐boron triple bond is bound to tellurate cations. The analysis allows the description of these salts as true π complexes between the B−B triple bond and the tellurium center. These complexes thus extend the well‐known Dewar‐Chatt‐Duncanson model of bonding to compounds made up solely of p block elements. Structural, spectroscopic and computational evidence is offered to argue that a set of recently reported heterocycles consisting of phenyltellurium cations complexed to diborynes bear all the hallmarks of \(\pi\)‐complexes in the \(\pi\)‐complex/metallacycle continuum envisioned by Joseph Chatt. Described as such, these compounds are unique in representing the extreme of a metal‐free continuum with conventional unsaturated three‐membered rings (cyclopropenes, azirenes, borirenes) occupying the opposite end.
KW  - boron
KW  - main group elements
KW  - solid-state NMR
KW  - \(\pi\) interactions
KW  - multiple bonds
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-214677
VL  - 15
IS  - 10
SP  - 1553
EP  - 1557
ER  -