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\(\pi\)‐Complexes of Diborynes with Main Group Atoms (2020)
Ewing, William C. ; Dellermann, Theresa ; Angel Wong, Y. T. ; Mattock, James D. ; Vargas, Alfredo ; Bryce, David L. ; Dewhurst, Rian D. ; Braunschweig, Holger
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.
Engineering a Small HOMO-LUMO Gap and Intramolecular B–B Hydroarylation by Diborene/Anthracene Orbital Intercalation (2017)
Wang, Sunewang R. ; Arrowsmith, Merle ; Böhnke, Julian ; Braunschweig, Holger ; Dellermann, Theresa ; Dewhurst, Rian D. ; Kelch, Hauke ; Krummenacher, Ivo ; Mattock, James D. ; Müssig, Jonas H. ; Thiess, Torsten ; Vargas, Alfredo ; Zhang, Jiji
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.
Diboryldiborenes: π‐Conjugated B\(_4\) Chains Isoelectronic to the Butadiene Dication (2018)
Hermann, Alexander ; Cid, Jessica ; Mattock, James D. ; Dewhurst, Rian D. ; Krummenacher, Ivo ; Vargas, Alfredo ; Ingleson, Michael J. ; Braunschweig, Holger
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.
Phosphine-Stabilized Diiododiborenes: Isolable Diborenes with Six Labile Bonds (2019)
Muessig, Jonas H. ; Thaler, Melanie ; Dewhurst, Rian D. ; Paprocki, Valerie ; Seufert, Jens ; Mattock, James D. ; Vargas, Alfredo ; Braunschweig, Holger
The lability of B=B, B-P and B-halide bonds is combined in the syntheses of the first diiododiborenes. In a series of reactivity tests, these diiododiborenes demonstrate cleavage of all six of their central bonds in different ways, leading to products of B=B hydrogenation and dihalogenation as well as halide exchange.
Isolation and Reactivity of an Antiaromatic s‐Block Metal Compound (2021)
Roy, Dipak Kumar ; Tröster, Tobias ; Fantuzzi, Felipe ; Dewhurst, Rian D. ; Lenczyk, Carsten ; Radacki, Krzysztof ; Pranckevicius, Conor ; Engels, Bernd ; Braunschweig, Holger
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.
{N ',N ''-Bis[2,6-bis(1-methylethyl)phenyl]-N,N-dimethylguanidinato-kappa N-2 ',N ''}dibromidoborane (2010)
Braunschweig, Holger ; Dewhurst, Rian D. ; Schwab, Katrin ; Wagner, Katharina
In the molecular structure of the title compound, C27H40N3BBr2, the B atom is connected to two bromide substituents and a guanidinate scaffold, forming a four– membered ring. An aryl group is connected to each N atom in the ring that contains two isopropyl groups in positions 2 and 6.
Tetraiododiborane(4) (B\(_2\)I\(_4\)) is a Polymer based on sp\(^3\) Boron in the Solid State (2020)
Muessig, Jonas H. ; Lisinetskaya, Polina ; Dewhurst, Rian D. ; Bertermann, Rüdiger ; Thaler, Melanie ; Mitric, Roland ; Braunschweig, Holger
Herein we present the first solid‐state structures of tetraiododiborane(4) (B\(_2\)I\(_4\)), which was long believed to exist in all phases as discrete molecules with planar, tricoordinate boron atoms, like the lighter tetrahalodiboranes(4) B\(_2\)F\(_4\), B\(_2\)Cl\(_4\), and B\(_2\)Br\(_4\). Single‐crystal X‐ray diffraction, solid‐state NMR, and IR measurements indicate that B\(_2\)I\(_4\) in fact exists as two different polymeric forms in the solid state, both of which feature boron atoms in tetrahedral environments. DFT calculations are used to simulate the IR spectra of the solution and solid‐state structures, and these are compared with the experimental spectra.
Toward Transition‐Metal‐Templated Construction of Arylated B\(_{4}\) Chains by Dihydroborane Dehydrocoupling (2019)
Lenczyk, Carsten ; Roy, Dipak Kumar ; Oberdorf, Kai ; Nitsch, Jörn ; Dewhurst, Rian D. ; Radacki, Krzysztof ; Halet, Jean-François ; Marder, Todd B. ; Bickelhaupt, Matthias ; Braunschweig, Holger
The reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH\(_{2}\)] (Dur=2,3,5,6‐Me\(_{4}\)C\(_{6}\)H) and [(Me\(_{3}\)Si)\(_{2}\)NBH\(_{2}\)] led to the formation of bridging borylene complexes of the form [(Cp\(^{*}\)RuH)\(_{2}\)BR] (Cp\(^{*}\)=C\(_{5}\)Me\(_{5}\); 1 a: R=Dur; 1 b: R=N(SiMe\(_{3}\))\(_{2}\)) through oxidative addition of the B−H bonds with concomitant hydrogen liberation. Employing the more electron‐deficient dihydroborane [3,5‐(CF\(_{3}\))\(_{2}\)‐C\(_{6}\)H\(_{3}\)BH\(_{2}\)] led to the formation of an anionic complex bearing a tetraarylated chain of four boron atoms, namely Li(THF)\(_{4}\)[(Cp\(^{*}\)Ru)\(_{2}\)B\(_{4}\)H\(_{5}\)(3,5‐(CF\(_{3}\))\(_{2}\)C\(_{6}\)H\(_{3}\))\(_{4}\)] (4), through an unusual, incomplete threefold dehydrocoupling process. A comparative theoretical investigation of the bonding in a simplified model of 4 and the analogous complex nido‐[1,2(Cp\(^{*}\)Ru)\(_{2}\)(μ‐H)B\(_{4}\)H\(_{9}\)] (I) indicates that there appear to be no classical σ‐bonds between the boron atoms in complex I, whereas in the case of 4 the B\(_{4}\) chain better resembles a network of three B−B σ bonds, the central bond being significantly weaker than the other two.
Mild synthesis of diboryldiborenes by diboration of B–B triple bonds (2019)
Brückner, Tobias ; Dewhurst, Rian D. ; Dellermann, Theresa ; Müller, Marcel ; Braunschweig, Holger
A set of diboryldiborenes are prepared by the mild, catalyst-free, room-temperature diboration of the B–B triple bonds of doubly base-stabilized diborynes. Two of the product diboryldiborenes are found to be air- and water-stable in the solid state, an effect that is attributed to their high crystallinity and extreme insolubility in a wide range of solvents.
Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donor (2017)
Auerhammer, Dominic ; Arrowsmith, Merle ; Braunschweig, Holger ; Dewhurst, Rian D. ; Jiménez-Halla, J. Oscar C. ; Kupfer, Thomas
The reaction of [(cAAC\(^{Me}\))BH\(_{3}\)] (cAAC\(^{Me}\) = 1-(2,6-iPr\(_{2}\)C\(_{6}\)H\(_{3}\))-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li\(^{+}\)[(cAAC\(^{Me}\)H)BH\(_{2}\)R]− (R = sp\(^{3}\)-, sp\(^{2}\)-, or sp-hybridised organic substituent), by migration of one boron-bound hydrogen atom to the adjacent carbene carbon of the cAAC ligand. A subsequent deprotonation/salt metathesis reaction with Me3SiCl or spontaneous LiH elimination yielded the neutral cAAC-supported mono(organo)boranes, [(cAAC\(^{Me}\)H)BH\(_{2}\)R]− (R]. Similarly the reaction of [cAAC\(^{Me}\))BH\(_{3}\)] with a neutral donor base L resulted in adduct formation by shuttling one boron-bound hydrogen to the cAAC ligand, to generate [(cAAC\(^{Me}\)H)BH\(_{2}\)L], either irreversibly (L = cAAC\(^{Me}\)) or reversibly (L = pyridine). Variable-temperature NMR data and DFT calculations on [(cAAC\(^{Me}\)H)BH\(_{2}\)(cAAC\(^{Me}\))] show that the hydrogen on the former carbene carbon atom exchanges rapidly with the boron-bound hydrides.
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