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  - 
TY  - JOUR
A1  - Matler, Alexander
A1  - Arrowsmith, Merle
A1  - Schorr, Fabian
A1  - Hermann, Alexander
A1  - Hofmann, Alexander
A1  - Lenczyk, Carsten
A1  - Braunschweig, Holger
T1  - Reactivity of Terminal Iron Borylenes and Bis(borylenes) with Carbodiimides: Cycloaddition, Metathesis, Insertion and C−H Activation Pathways
JF  - European Journal of Inorganic Chemistry
N2  - The reactions of carbodiimides with the iron arylborylene complex [Fe=BDur(CO)\(_{3}\)(PMe\(_{3}\))] (Dur=2,3,5,6-Me\(_{4}\)C\(_{6}\)H) and the iron bis(borylene) complex [Fe{=BDur}{=BN(SiMe\(_{3}\))\(_{2}\)}(CO)\(_{3}\)] yield a wide variety of temperature-dependent products, including known FeBNC and novel FeBNB metallacycles, complexes of N-heterocyclic boracarbene and spiro-boracarbene ligands and a unique 1,3,2,4-diazadiborolyl pianostool complex, characterized by NMR spectroscopy and X-ray crystallography. The product distributions can be rationalized by considering sequences of cycloaddition, metathesis, insertion, and C−H activation pathways mainly governed by sterics.
KW  - structure elucidation
KW  - borylene complexes
KW  - cycloaddition
KW  - metathesis
KW  - reaction mechanisms
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-257397
VL  - 2021
IS  - 45
ER  -