RESUMEN
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.
RESUMEN
A novel thiophene-bridged donor-acceptor system was synthesized with a carbazole as donor and a borole as acceptor unit. The borole group was successfully installed via the tin-boron exchange reaction of 1,1-dimethyl-2,3,4,5-tetraphenylstannole with 9-(5-(dibromoboryl)thiophen-2-yl)carbazole. The effect of the borole on the optoelectronic properties of the donor-acceptor system was explored by spectroscopic (UV/Vis and fluorescence spectroscopy), electrochemical (cyclic voltammetry) and theoretical (TD-DFT) methods as well as by modifying its structure. The corresponding donor-acceptor compound bearing the widely employed dimesitylboryl acceptor group was also synthesized for comparison.
RESUMEN
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[double bond, length as m-dash]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.
RESUMEN
A series of NHC-supported 1,2-dithienyldiborenes was synthesized from the corresponding (dihalo)thienylborane NHC precursors. NMR and UV/Vis spectroscopic data, as well as X-ray crystallographic analyses, were used to assess the electronic and steric influences on the B=B double bond of various NHCs and electron-donating substituents on the thienyl ligands. Crystallographic data showed that the degree of coplanarity of the diborene core and thienyl groups is highly dependent on the sterics of the substituents. Furthermore, any increase in the electron-donating ability of the substituents resulted in the destabilization of the HOMO and greater instability of the resulting diborenes.
RESUMEN
The reaction of [(cAACMe)BH3] (cAACMe = 1-(2,6-iPr2C6H3)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li+[(cAACMeH)BH2R]- (R = sp3-, sp2-, 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, [(cAACMe)BH2R]. Similarly the reaction of [(cAACMe)BH3] with a neutral donor base L resulted in adduct formation by shuttling one boron-bound hydrogen to the cAAC ligand, to generate [(cAACMeH)BH2L], either irreversibly (L = cAACMe) or reversibly (L = pyridine). Variable-temperature NMR data and DFT calculations on [(cAACMeH)BH2(cAACMe)] show that the hydrogen on the former carbene carbon atom exchanges rapidly with the boron-bound hydrides.
RESUMEN
The base-stabilized borylene [Cp(OC)2 Mn=BtBu(IMe)] readily reacts with elemental chalcogens in an insertion reaction that yields borachalcone complexes [Cp(OC)2 Mn-E=BtBu(IMe)] (E=S, Se, Te). The tellurium example features the first double bond between boron and tellurium, making Te the heaviest main-group element to make multiple bonds with boron. This unprecedented interaction has been fully investigated both experimentally and computationally.
RESUMEN
Deprotonation of [(cAAC)BH2 (CN)] provided clean access to the stable boryl anion, [(cAAC)BH(CN)]- . Whereas the addition of soft electrophiles occurred at the nucleophilic boron center, harder silyl electrophiles added to the harder terminal cyano nitrogen. The resulting [(cAAC)BH(CNSiPh3 )] species behaved like a silylium boryl nucleophile as well as a neutral silylisonitrile borylene.
RESUMEN
Reduction of carbene-borane adduct [(cAAC)BBr2 (CN)] (cAAC=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) cleanly yielded the tetra(cyanoborylene) species [(cAAC)B(CN)]4 presenting a 12-membered (BCN)4 ring. The analysis of the Kohn-Sham molecular orbitals showed significant borylene character of the BI atoms. [(cAAC)B(CN)]4 was found to reduce two equivalents of AgCN per boron center to yield [(cAAC)B(CN)3 ] and fragmented into two-coordinate boron(I) units upon reaction with IMeMe (1,3,4,5-tetramethylimidazol-2-ylidene) to yield the corresponding tricoordinate mixed cAAC-NHC cyanoborylene. The analogous cAAC-phosphine cyanoborylene was obtained by reduction of [(cAAC)BBr2 (CN)] in the presence of excess phosphine.
RESUMEN
Silylenes: Reaction of the donor-stabilized silylene 1 with elemental sulfur, selenium, or tellurium led to the formation of 2 a-c [SiN(4)X skeletons (X = S, Se, Te)], the first stable five-coordinate silicon(IV) compounds with silicon-chalcogen double bonds (see figure).