Synthesis and structures of molecular beryllium Grignard analogues featuring terminal and bridging pseudohalides.

The carbene-stabilised beryllium Grignards [(CAAC)BeBrR] (R = CAACH 1a, Dur 1b; CAAC/H = 1-(2,6-dipropylphenyl)-2,2,4,4-tetramethylpyrrolidin-2-yl/idene; Dur = 2,3,5,6-tetramethylphenyl) undergo salt metathesis with various pseudohalide salt precursors. Whereas with [NaNCS] the thiocyanato Grignards [(CAAC)Be(NCS)R] (R = CAACH 2a, Dur 2b) are obtained selectively, salt metatheses with [Na(OCP)(dioxane)] and [K(OCN)] are fraught with side reactions, in particular scrambling of both neutral and anionic ligands, leading to complex product mixtures, from which the first examples of beryllium phosphaethynolate Grignards [(thf)(CAACH)Be(OCP)] (3) and [(CAAC)Be(OCP)R] (R = CAACH 4a, Dur 4b), as well as the isocyanate-bridged hexamer [(CAAC)BrBe(1,3-μ-OCN)] (7) were determined as the main products. The complexity of possible side reactions is seen in complex 5, a byproduct of the salt metathesis of 1b with [Na(OCP)(dioxane)], which hints at radical redox processes, OCP homocoupling, OCP coupling with CAAC, as well as OCP insertion into the Be-R bond.

Transition-metal-like coordination chemistry of dicoordinate borylenes with organic azides.

The photolytic or oxidative liberation of a cyclic (amino)(alkyl)carbene (CAAC)-stabilized arylborylene in the presence of organoazides yielded borylene-organoazide complexes (4a,b) has been achieved in a manner akin to the first step of the Staudinger reaction. Similarly, a CAAC-stabilized aminoborylene also afforded borylene-organoazide complexes (6a-c), which further undergo rearrangement to produce aminoborane triazene species (7a,b).

Coordination-induced reductive elimination from a titanium(IV) complex.

Diamidopyridine-supported titanium dibenzyl complexes undergo coordination-induced C-C reductive elimination upon addition of alkynes and quantitative formation of titanacyclopentadienes. The distinct radical mechanism of this reductive mechanism gives new insights into C-C bond formation with titanium.

Synthesis and Reactivity of Tricoordinate Organoberyllium Azides.

A series of terminal mono- and disubstituted beryllium azides of the form [(CAAC)Be(N)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 [LBe(N)] (L=CAACNH=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-imine, IiPr=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.

Tricoordinate Beryllium Radicals and Their Reactivity.

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)(EtO)BeDur] (), which undergoes a facile second one-electron reduction concomitant with the insertion of the beryllium center into the endocyclic C-N bond and a cyclopropane-forming C-H bond activation of an adjacent methyl group. generation of and addition of PMe yield the stable analogue, [(CAAC)(MeP)BeDur] (), which serves as a platform for PMe-ligand exchange with stronger donors, generating the radicals [(CAAC)LBeDur] (, L = isocyanides, pyridines, and -heterocyclic carbenes). X-ray structural analyses show trigonal-planar beryllium centers and strong π backbonding from the metal to the CAAC ligand.

Synthesis, Structural Characterization, and Bonding of Molecular Heavier Beryllium Chalcogenides.

The reactions of a cyclic alkyl(amino)carbene (CAAC)-stabilized beryllium radical with E Ph (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.

A Neutral Beryllium(I) Radical.

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.