TY  - JOUR
A1  - Huang, Zhenguo
A1  - Wang, Suning
A1  - Dewhurst, Rian D.
A1  - Ignat'ev, Nikolai V.
A1  - Finze, Maik
A1  - Braunschweig, Holger
T1  - Boron: Its Role in Energy‐Related Processes and Applications
JF  - Angewandte Chemie International Edition
N2  - Boron's unique position in the Periodic Table, that is, at the apex of the line separating metals and nonmetals, makes it highly versatile in chemical reactions and applications. Contemporary demand for renewable and clean energy as well as energy‐efficient products has seen boron playing key roles in energy‐related research, such as 1) activating and synthesizing energy‐rich small molecules, 2) storing chemical and electrical energy, and 3) converting electrical energy into light. These applications are fundamentally associated with boron's unique characteristics, such as its electron‐deficiency and the availability of an unoccupied p orbital, which allow the formation of a myriad of compounds with a wide range of chemical and physical properties. For example, boron's ability to achieve a full octet of electrons with four covalent bonds and a negative charge has led to the synthesis of a wide variety of borate anions of high chemical and electrochemical stability—in particular, weakly coordinating anions. This Review summarizes recent advances in the study of boron compounds for energy‐related processes and applications.
KW  - boron
KW  - electrolytes
KW  - hydrogen
KW  - OLEDs
KW  - small-molecule activation
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-218514
VL  - 59
IS  - 23
SP  - 8800
EP  - 8816
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  - Härterich, Marcel
A1  - Matler, Alexander
A1  - Dewhurst, Rian D.
A1  - Sachs, Andreas
A1  - Oppel, Kai
A1  - Stoy, Andreas
A1  - Braunschweig, Holger
T1  - A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl
JF  - Nature Communications
N2  - The Fischer carbene synthesis, involving the conversion of a transition metal (TM)-bound CO ligand to a carbene ligand of the form [=C(OR’)R] (R, R’ = organyl groups), is one of the seminal reactions in the history of organometallic chemistry. Carbonyl complexes of p-block elements, of the form [E(CO)n] (E = main-group fragment), are much less abundant than their TM cousins; this scarcity and the general instability of low-valent p-block species means that replicating the historical reactions of TM carbonyls is often very difficult. Here we present a step-for-step replica of the Fischer carbene synthesis at a borylene carbonyl involving nucleophilic attack at the carbonyl carbon followed by electrophilic quenching at the resultant acylate oxygen atom. These reactions provide borylene acylates and alkoxy-/silyloxy-substituted alkylideneboranes, main-group analogues of the archetypal transition metal acylate and Fischer carbene families, respectively. When either the incoming electrophile or the boron center has a modest steric profile, the electrophile instead attacks at the boron atom, leading to carbene-stabilized acylboranes – boron analogues of the well-known transition metal acyl complexes. These results constitute faithful main-group replicas of a number of historical organometallic processes and pave the way to further advances in the field of main-group metallomimetics.
KW  - chemical bonding
KW  - ligands
Y1  - 2023
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-357270
VL  - 14
ER  -