RESUMEN
A series of terminal mono- and disubstituted beryllium azides of the form [(CAAC)Be(N3)R] (R=CAACH, Dur; CAACH/CAAC=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-yl/idene, Dur=2,3,5,6-tetramethylphenyl) and [L2Be(N3)2] (L=CAACNH=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-imine, IiPrMe=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene), respectively, were synthesized and characterized by NMR spectroscopy and X-ray crystallography. Thermolysis and photolysis products of these first examples of tricoordinate azidoberyllium complexes evidence extensive ligand scrambling and the formal insertion of nitrenes into the CAAC-Be bond, generating cyclic alkyl(amino)imine (CAAI) ligands. Furthermore, the reaction with a small N-heterocyclic carbene (NHC) leads to unexpected CAAC-NHC ligand exchange, while the reaction with pentaphenylborole yields the first γ-azide adduct of a borole, long postulated to be the first step in the synthesis of 1,2-azaborinines from boroles and azides.
RESUMEN
The one-electron reduction of [(CAAC)Be(Dur)Br] (CAAC = cyclic alkyl(amino)carbene, Dur = 2,3,5,6-tetramethylphenyl = duryl) with lithium sand in diethyl ether yields the first neutral, tricoordinate, and moderately stable beryllium radical, [(CAAC)(Et2O)BeDur]⢠(2-Et2O), which undergoes a facile second one-electron reduction concomitant with the insertion of the beryllium center into the endocyclic C-NCAAC bond and a cyclopropane-forming C-H bond activation of an adjacent methyl group. In situ generation of 2-Et2O and addition of PMe3 yield the stable analogue, [(CAAC)(Me3P)BeDur]⢠(2-PMe3), which serves as a platform for PMe3-ligand exchange with stronger donors, generating the radicals [(CAAC)LBeDur]⢠(2-L, L = isocyanides, pyridines, and N-heterocyclic carbenes). X-ray structural analyses show trigonal-planar beryllium centers and strong π backbonding from the metal to the CAAC ligand. The EPR signals of all six isolated [(CAAC)LBeDur]⢠radicals display significant, albeit small, hyperfine coupling to the 9Be nucleus. DFT calculations show that the spin density is mostly delocalized over the CAAC π framework and, where present, the isocyanide CN moiety, with only a small proportion (3-6%) on the beryllium center. 2-PMe3 proved thermally unstable at 80 °C, first undergoing radical hydrogen abstraction with the solvent, followed by insertion of beryllium into the endocyclic C-NCAAC bond and PMe3 transfer to the former carbene carbon atom. The reactions with diphenyl disulfide and phenyl azide occur at the beryllium center and yield the corresponding Be(II) phenyl sulfide and amino complexes, respectively, the latter concomitant with radical transfer and hydrogen abstraction by the beryllium-bound nitrogen center.
RESUMEN
The reactions of a cyclic alkyl(amino)carbene (CAAC)-stabilized beryllium radical with E2 Ph2 (E=S, Se, Te) and of a beryllole with HEPh (E=S, Se) yield the corresponding beryllium phenylchalcogenides, including the first structurally authenticated beryllium selenide and telluride complexes. Calculations show that their Be-E bonds are best described by the interaction between the Be+ and E- fragments, with Coulombic forces accounting for ca. 55 % of the attraction and orbital interactions dominated by the σ component.
RESUMEN
The reduction of a cyclic alkyl(amino)carbene (CAAC)-stabilized organoberyllium chloride yields the first neutral beryllium radical, which was characterized by EPR, IR, and UV/Vis spectroscopy, X-ray crystallography, and DFT calculations.
