@article{BruecknerFantuzziStennettetal.2021,
  author    = {Br{\"u}ckner, Tobias and Fantuzzi, Felipe and Stennett, Tom E. and Krummenacher, Ivo and Dewhurst, Rian D. and Engels, Bernd and Braunschweig, Holger},
  title     = {Isolation of neutral, mono-, and dicationic B\(_2\)P\(_2\) rings by diphosphorus addition to a boron-boron triple bond},
  series = {Angewandte Chemie International Edition},
  volume    = {60},
  journal   = {Angewandte Chemie International Edition},
  number    = {24},
  doi       = {10.1002/anie.202102218},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256451},
  pages     = {13661-13665},
  year      = {2021},
  abstract  = {The NHC-stabilised diboryne (B\(_2\)(SIDep)\(_2\); SIDep=1,3-bis(2,6-diethylphenyl)imidazolin-2-ylidene) undergoes a high-yielding P-P bond activation with tetraethyldiphosphine at room temperature to form a B\(_2\)P\(_2\) heterocycle via a diphosphoryldiborene by 1,2-diphosphination. The heterocycle can be oxidised to a radical cation and a dication, respectively, depending on the oxidant used and its counterion. Starting from the planar, neutral 1,3-bis(alkylidene)-1,3-diborata-2,4-diphosphoniocyclobutane, each oxidation step leads to decreased B-B distances and loss of planarity by cationisation. X-ray analyses in conjunction with DFT and CASSCF/NEVPT2 calculations reveal closed-shell singlet, butterfly-shaped structures for the NHC-stabilised dicationic B\(_2\)P\(_2\) rings, with their diradicaloid, planar-ring isomers lying close in energy.},
  language  = {en}
}
@unpublished{BoehnkeDellermannCeliketal.2018,
  author    = {B{\"o}hnke, Julian and Dellermann, Theresa and Celik, Mehmet Ali and Krummenacher, Ivo and Dewhurst, Rian D. and Demeshko, Serhiy and Ewing, William C. and Hammond, Kai and Heß, Merlin and Bill, Eckhard and Welz, Eileen and R{\"o}hr, Merle I. S. and Mitric, Roland and Engels, Bernd and Meyer, Franc and Braunschweig, Holger},
  title     = {Isolation of diradical products of twisted double bonds},
  series = {Nature Communications},
  journal   = {Nature Communications},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-160248},
  year      = {2018},
  abstract  = {Molecules containing multiple bonds between atoms—most often in the form of olefins—are ubiquitous in nature, commerce, and science, and as such have a huge impact on everyday life. Given their prominence, over the last few decades, frequent attempts have been made to perturb the structure and reactivity of multiply-bound species through bending and twisting. However, only modest success has been achieved in the quest to completely twist double bonds in order to homolytically cleave the associated π bond. Here, we present the isolation of double-bond-containing species based on boron, as well as their fully twisted diradical congeners, by the incorporation of attached groups with different electronic properties. The compounds comprise a structurally authenticated set of diamagnetic multiply-bound and diradical singly-bound congeners of the same class of compound.},
  language  = {en}
}
@article{BoehnkeDellermannCeliketal.2018,
  author    = {B{\"o}hnke, Julian and Dellermann, Theresa and Celik, Mehmet Ali and Krummenacher, Ivo and Dewhurst, Rian D. and Demeshko, Serhiy and Ewing, William C. and Hammond, Kai and Heß, Merlin and Bill, Eckhard and Welz, Eileen and R{\"o}hr, Merle I. S. and Mitric, Roland and Engels, Bernd and Meyer, Franc and Braunschweig, Holger},
  title     = {Isolation of diborenes and their 90°-twisted diradical congeners},
  series = {Nature Communications},
  volume    = {9},
  journal   = {Nature Communications},
  number    = {Article number: 1197},
  doi       = {10.1038/s41467-018-02998-3},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-160431},
  year      = {2018},
  abstract  = {Molecules containing multiple bonds between atoms—most often in the form of olefins—are ubiquitous in nature, commerce, and science, and as such have a huge impact on everyday life. Given their prominence, over the last few decades, frequent attempts have been made to perturb the structure and reactivity of multiply-bound species through bending and twisting. However, only modest success has been achieved in the quest to completely twist double bonds in order to homolytically cleave the associated π bond. Here, we present the isolation of double-bond-containing species based on boron, as well as their fully twisted diradical congeners, by the incorporation of attached groups with different electronic properties. The compounds comprise a structurally authenticated set of diamagnetic multiply-bound and diradical singly-bound congeners of the same class of compound.},
  language  = {en}
}
@article{RoyTroesterFantuzzietal.2021,
  author    = {Roy, Dipak Kumar and Tr{\"o}ster, Tobias and Fantuzzi, Felipe and Dewhurst, Rian D. and Lenczyk, Carsten and Radacki, Krzysztof and Pranckevicius, Conor and Engels, Bernd and Braunschweig, Holger},
  title     = {Isolation and Reactivity of an Antiaromatic s-Block Metal Compound},
  series = {Angewandte Chemie International Edition},
  volume    = {60},
  journal   = {Angewandte Chemie International Edition},
  number    = {7},
  doi       = {10.1002/anie.202014557},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-224447},
  pages     = {3812 -- 3819},
  year      = {2021},
  abstract  = {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.},
  language  = {en}
}
@unpublished{WangArrowsmithBoehnkeetal.2017,
  author    = {Wang, Sunewang R. and Arrowsmith, Merle and B{\"o}hnke, Julian and Braunschweig, Holger and Dellermann, Theresa and Dewhurst, Rian D. and Kelch, Hauke and Krummenacher, Ivo and Mattock, James D. and M{\"u}ssig, Jonas H. and Thiess, Torsten and Vargas, Alfredo and Zhang, Jiji},
  title     = {Engineering a Small HOMO-LUMO Gap and Intramolecular B-B Hydroarylation by Diborene/Anthracene Orbital Intercalation},
  series = {Angewandte Chemie, International Edition},
  volume    = {56},
  journal   = {Angewandte Chemie, International Edition},
  number    = {27},
  doi       = {10.1002/anie.201704063},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-148126},
  pages     = {8009-8013},
  year      = {2017},
  abstract  = {The diborene 1 was synthesized by reduction of a mixture of 1,2-di-9-anthryl-1,2-dibromodiborane(4) (6) and trimethylphosphine with potassium graphite. The X-ray structure of 1 shows the two anthryl rings to be parallel and their π(C\(_{14}\)) systems perpendicular to the diborene π(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying π(B=B) orbital and the low-lying π* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO-LUMO gap (HLG) and ultimately an unprecedented anthryl B-B bond hydroarylation. The HLG of 1 was estimated to be 1.57 eV from the onset of the long wavelength band in its UV-vis absorption spectrum (THF, λ\(_{onset}\) = 788 nm). The oxidation of 1 with elemental selenium afforded diboraselenirane 8 in quantitative yield. By oxidative abstraction of one phosphine ligand by another equivalent of elemental selenium, the B-B and C\(^1\)-H bonds of 8 were cleaved to give the cyclic 1,9-diboraanthracene 9.},
  language  = {en}
}
@article{CuiDietzHaerterichetal.2021,
  author    = {Cui, Jingjing and Dietz, Maximilian and H{\"a}rterich, Marcel and Fantuzzi, Felipe and Lu, Wei and Dewhurst, Rian D. and Braunschweig, Holger},
  title     = {Diphosphino-Functionalized 1,8-Naphthyridines: a Multifaceted Ligand Platform for Boranes and Diboranes},
  series = {Chemistry—A European Journal},
  volume    = {27},
  journal   = {Chemistry—A European Journal},
  number    = {63},
  doi       = {10.1002/chem.202102721},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256994},
  pages     = {15751-15756},
  year      = {2021},
  abstract  = {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.},
  language  = {en}
}
@unpublished{HermannCidMattocketal.2018,
  author    = {Hermann, Alexander and Cid, Jessica and Mattock, James D. and Dewhurst, Rian D. and Krummenacher, Ivo and Vargas, Alfredo and Ingleson, Michael J. and Braunschweig, Holger},
  title     = {Diboryldiborenes: π-Conjugated B\(_4\) Chains Isoelectronic to the Butadiene Dication},
  series = {Angewandte Chemie, International Edition},
  journal   = {Angewandte Chemie, International Edition},
  doi       = {10.1002/anie.201805394},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-167977},
  year      = {2018},
  abstract  = {sp\(^2\)-sp\(^3\) diborane species based on bis(catecholato)diboron and N-heterocyclic carbenes (NHCs) are subjected to catechol/bromide exchange selectively at the sp\(^3\) boron atom. The reduction of the resulting 1,1-dibromodiborane adducts led to reductive coupling and isolation of doubly NHC-stabilized 1,2-diboryldiborenes. These compounds are the first examples of molecules exhibiting pelectron delocalization over an all-boron chain.},
  language  = {en}
}
@article{MuessigLisinetskayaDewhurstetal.2020,
  author    = {Muessig, Jonas H. and Lisinetskaya, Polina and Dewhurst, Rian D. and Bertermann, R{\"u}diger and Thaler, Melanie and Mitric, Roland and Braunschweig, Holger},
  title     = {Dibortetraiodid (B\(_2\)I\(_4\)) ist im Festk{\"o}rper ein Polymer aus sp3-hybridisiertem Bor},
  series = {Angewandte Chemie},
  volume    = {132},
  journal   = {Angewandte Chemie},
  number    = {14},
  doi       = {10.1002/ange.201913590},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-219653},
  pages     = {5574-5579},
  year      = {2020},
  abstract  = {Anhand der ersten Festk{\"o}rperstrukturen von Dibortetraiodid (B\(_2\)I\(_4\)) wird gezeigt, dass dieses nicht, wie lange angenommen, analog zu den leichteren Dibortetrahalogeniden B\(_2\)F\(_4\), B\(_2\)Cl\(_4\) und B\(_2\)Br\(_4\) in allen Aggregatzust{\"a}nden in Form diskreter Molek{\"u}le mit planaren, dreifach koordinierten Boratomen vorliegt. R{\"o}ntgenstrukturanalysen, Festk{\"o}rper-NMR- und IR-Messungen zeigen, dass B\(_2\)I\(_4\) im Festk{\"o}rper in zwei polymeren Konformeren vorkommt, die tetraedrisch koordinierte Boratome enthalten. Anhand von DFT-Rechnungen werden die IR-Spektren in L{\"o}sung und im Festk{\"o}rper simuliert und mit den experimentellen Daten verglichen.},
  language  = {de}
}
@article{SchorrSchopperRienschetal.2021,
  author    = {Schorr, Fabian and Schopper, Nils and Riensch, Nicolas and Fantuzzi, Felipe and Neder, Marco and Dewhurst, Rian D. and Thiess, Thorsten and Br{\"u}ckner, Tobias and Hammond, Kai and Helten, Holger and Finze, Maik and Braunschweig, Holger},
  title     = {Controlled Synthesis of Oligomers Containing Main-Chain B(sp\(^{2}\))-B(sp\(^{2}\)) Bonds},
  series = {Chemistry—A European Journal},
  volume    = {27},
  journal   = {Chemistry—A European Journal},
  number    = {64},
  doi       = {10.1002/chem.202103366},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-257274},
  pages     = {16043-16048},
  year      = {2021},
  abstract  = {A number of novel alkynyl-functionalized diarylbis(dimethylamino)diboranes(4) are prepared by salt metathesis, and the appended alkynyl groups are subjected to hydroboration. Their reactions with monohydroboranes lead to discrete boryl-appended diborane(4) species, while dihydroboranes induce their catenation to oligomeric species, the first known examples of well-characterized macromolecular species with B-B bonds. The oligomeric species were found to comprise up to ten repeat units and are soluble in common organic solvents. Some of the oligomeric species have good air stability and all were characterized by NMR and vibrational spectroscopy and size-exclusion chromatography techniques.},
  language  = {en}
}
@unpublished{StoyBoehnkeJiménezHallaetal.2018,
  author    = {Stoy, Andreas and B{\"o}hnke, Julian and Jiménez-Halla, J. Oscar C. and Dewhurst, Rian D. and Thiess, Torsten and Braunschweig, Holger},
  title     = {CO\(_2\) Binding and Splitting by Boron-Boron Multiple Bonds},
  series = {Angewandte Chemie, International Edition},
  journal   = {Angewandte Chemie, International Edition},
  doi       = {10.1002/anie.201802117},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-164265},
  year      = {2018},
  abstract  = {CO\(_2\) is found to undergo room-temperature, ambient- pressure reactions with two species containing boron-boron multiple bonds, leading to incorporation of either one or two CO\(_2\) molecules. In one case, a thermally-unstable intermediate was structurally characterized, indicating the operation of an initial 2+2 cycloaddition mechanism in the reaction.},
  language  = {en}
}
@unpublished{AuerhammerArrowsmithBoehnkeetal.2018,
  author    = {Auerhammer, Dominic and Arrowsmith, Merle and B{\"o}hnke, Julian and Braunschweig, Holger and Dewhurst, Rian D. and Kupfer, Thomas},
  title     = {Brothers from Another Mother: a Borylene and its Dimer are Non-Interconvertible but Connected through Reactivity},
  series = {Chemical Science},
  journal   = {Chemical Science},
  doi       = {10.1039/C7SC04789D},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-157125},
  year      = {2018},
  abstract  = {The self-stabilizing, tetrameric cyanoborylene [(cAAC)B(CN)]4 (I, cAAC = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) and its diborene relative, [(cAAC)(CN)B=B(CN)(cAAC)] (II), both react with disulfides and diselenides to yield the corresponding cAAC-supported cyanoboron bis(chalcogenides). Furthermore, reactions of I or II with elemental sulfur and selenium in various stoichiometries provided access to a variety of cAAC- stabilized cyanoboron-chalcogen heterocycles, including a unique dithiaborirane, a diboraselenirane, 1,3-dichalcogena-2,4-diboretanes, 1,3,4-trichalcogena- 2,5-diborolanes and a rare six-membered 1,2,4,5-tetrathia-3,6-diborinane. Stepwise addition reactions and solution stability studies provided insights into the mechanism of these reactions and the subtle differences in reactivity observed between I and II.},
  language  = {en}
}
@article{HuangWangDewhurstetal.2020,
  author    = {Huang, Zhenguo and Wang, Suning and Dewhurst, Rian D. and Ignat'ev, Nikolai V. and Finze, Maik and Braunschweig, Holger},
  title     = {Boron: Its Role in Energy-Related Processes and Applications},
  series = {Angewandte Chemie International Edition},
  volume    = {59},
  journal   = {Angewandte Chemie International Edition},
  number    = {23},
  doi       = {10.1002/anie.201911108},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-218514},
  pages     = {8800 -- 8816},
  year      = {2020},
  abstract  = {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.},
  language  = {en}
}
@article{GaertnerMarekArrowsmithetal.2021,
  author    = {G{\"a}rtner, Annalena and Marek, Matth{\"a}us and Arrowsmith, Merle and Auerhammer, Dominic and Radacki, Krzysztof and Prieschl, Dominic and Dewhurst, Rian D. and Braunschweig, Holger},
  title     = {Boron- versus Nitrogen-Centered Nucleophilic Reactivity of (Cyano)hydroboryl Anions: Synthesis of Cyano(hydro)organoboranes and 2-Aza-1,4-diborabutatrienes},
  series = {Chemistry—A European Journal},
  volume    = {27},
  journal   = {Chemistry—A European Journal},
  number    = {37},
  doi       = {10.1002/chem.202101025},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256853},
  pages     = {9694-9699},
  year      = {2021},
  abstract  = {Cyclic alkyl(amino)carbene-stabilized (cyano)hydroboryl anions were synthesized by deprotonation of (cyano)dihydroborane precursors. While they display boron-centered nucleophilic reactivity towards organohalides, generating fully unsymmetrically substituted cyano(hydro)organoboranes, they show cyano-nitrogen-centered nucleophilic reactivity towards haloboranes, resulting in the formation of hitherto unknown linear 2-aza-1,4-diborabutatrienes.},
  language  = {en}
}
@article{LuJayaramanFantuzzietal.2022,
  author    = {Lu, Wei and Jayaraman, Arumugam and Fantuzzi, Felipe and Dewhurst, Rian D. and H{\"a}rterich, Marcel and Dietz, Maximilian and Hagspiel, Stephan and Krummenbacher, Ivo and Hammond, Kai and Cui, Jingjing and Braunschweig, Holger},
  title     = {An unsymmetrical, cyclic diborene based on a chelating CAAC ligand and its small-molecule activation and rearrangement chemistry},
  series = {Angewandte Chemie International Edition},
  volume    = {61},
  journal   = {Angewandte Chemie International Edition},
  number    = {3},
  doi       = {10.1002/anie.202113947},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256576},
  year      = {2022},
  abstract  = {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.},
  language  = {en}
}
@article{HagspielFantuzziDewhurstetal.2021,
  author    = {Hagspiel, Stephan and Fantuzzi, Felipe and Dewhurst, Rian D. and G{\"a}rtner, Annalena and Lindl, Felix and Lamprecht, Anna and Braunschweig, Holger},
  title     = {Addukte des Stammboraphosphaketens H\(_{2}\)BPCO und deren Insertionsreaktionen mittels Decarbonylierung},
  series = {Angewandte Chemie},
  volume    = {133},
  journal   = {Angewandte Chemie},
  number    = {24},
  doi       = {10.1002/ange.202103521},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-244803},
  pages     = {13780 -- 13784},
  year      = {2021},
  abstract  = {Die ersten Beispiele f{\"u}r 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 f{\"u}r 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 best{\"a}tigt.},
  language  = {de}
}
@article{HagspielFantuzziDewhurstetal.2021,
  author    = {Hagspiel, Stephan and Fantuzzi, Felipe and Dewhurst, Rian D. and G{\"a}rtner, Annalena and Lindl, Felix and Lamprecht, Anna and Braunschweig, Holger},
  title     = {Adducts of the parent boraphosphaketene H\(_2\)BPCO and their decarbonylative insertion chemistry},
  series = {Angewandte Chemie International Edition},
  volume    = {60},
  journal   = {Angewandte Chemie International Edition},
  number    = {24},
  doi       = {10.1002/anie.202103521},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256470},
  pages     = {13666-13670},
  year      = {2021},
  abstract  = {The first examples of Lewis base adducts of the parent boraphosphaketene (H\(_2\)B-PCO) and their cyclodimers are prepared. One of these adducts is shown to undergo mild decarbonylation and phosphinidene insertion into a B-C bond of a borole, forming very rare examples of 1,2-phosphaborinines, B/P isosteres of benzene. The strong donor properties of these 1,2-phosphaborinines are confirmed by the synthesis of their π complexes with the Group 6 metals.},
  language  = {en}
}
@article{HaerterichMatlerDewhurstetal.2023,
  author    = {H{\"a}rterich, Marcel and Matler, Alexander and Dewhurst, Rian D. and Sachs, Andreas and Oppel, Kai and Stoy, Andreas and Braunschweig, Holger},
  title     = {A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl},
  series = {Nature Communications},
  volume    = {14},
  journal   = {Nature Communications},
  doi       = {10.1038/s41467-023-36251-3},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-357270},
  year      = {2023},
  abstract  = {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.},
  language  = {en}
}
@article{EwingDellermannAngelWongetal.2020,
  author    = {Ewing, William C. and Dellermann, Theresa and Angel Wong, Y. T. and Mattock, James D. and Vargas, Alfredo and Bryce, David L. and Dewhurst, Rian D. and Braunschweig, Holger},
  title     = {\(\pi\)-Complexes of Diborynes with Main Group Atoms},
  series = {Chemistry - An Asian Journal},
  volume    = {15},
  journal   = {Chemistry - An Asian Journal},
  number    = {10},
  doi       = {10.1002/asia.202000185},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-214677},
  pages     = {1553 -- 1557},
  year      = {2020},
  abstract  = {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.},
  language  = {en}
}