Beryllium-centred C–H activation of benzene

Abstract

Reaction of BeCl2 with the dilithium diamide, [{SiNDipp}Li2] ({SiNDipp} = {CH2SiMe2NDipp}2), provides the dimeric chloroberyllate, [{SiNDippBeCl)Li]2, en route to the 2-coordinate beryllium amide, [SiNDippBe]. Lithium or sodium reduction of [SiNDippBe]...

Linear BeNCO and OBeNC: kinetically stable neutral Be-bearing free molecules

“…The Be–N bond distance in BeNCO is 1.4884 Å, which is slightly shorter than those of the experimentally available two-coordinate complexes (2,6-Mes 2 C 6 H 3 )BeN(SiMe 3 ) 2 ( I ) 17 and Be[N(SiMe 3 ) 2 ] 2 ( II ) 68 and the seven-membered ring complex BeN(dipp)Si(Me 2 )CH = CHSi(Me 2 )N(dipp) ( III ), 12 (1.5075, 1.5121, and 1.5072 Å, respectively), as well as the theoretical Be–N double bond length of 1.50 Å, 69 but significantly longer than the computed Be–N bond length of 1.4604 Å in the experimentally identified complex RNBeN(SiMe 3 )NR ( IV , R = 1-dipp-3,3-diethyl-5,5-dimethylpyrrolidin-2-ylidene) 7 and the theoretical Be–N triple bond length (1.390 Å). 69 Note that the experimentally available Be–N bond lengths determined by XRD are in the range of 1.515–1.519 Å in I , II , and III 12,17,68 and 1.464 Å in IV , 7 very close to the present theoretically computed values (Fig. S3, ESI†).…”

“…1–5 This is because constructing these interesting beryllium bonds will help not only in building more stable beryllium complexes and materials, but also in deeply understanding the bonding nature of beryllium bonds. 6–12…”

“…[1][2][3][4][5] This is because constructing these interesting beryllium bonds will help not only in building more stable beryllium complexes and materials, but also in deeply understanding the bonding nature of beryllium bonds. [6][7][8][9][10][11][12] Beryllium is a special s-zone metal element. Compared with other alkaline earth metals, its higher electronegativity makes its bonding mode highly complex.…”

Ligand exchange at tetra-coordinated beryllium centres

“…[21][22][23][24][25][26] Directed synthetic routes to industrial relevant beryllium compounds like alkoxides have been developed 27 and beryllium-centred C-H bond activation under reducing conditions has been achieved. 28 Due to the small size of the beryllium atom, ligands commonly employed in group 2 chemistry are often too bulky and steric effects have decisive influence on the reactivity of beryllium complexes. 29 This frequently leads to ligand and solvent activation, [30][31][32][33][34][35] while also the influence of different very similar and simple ligands, like halides, should not be underestimated.…”

Beryllium compounds for the carbon–halogen bond activation of phenyl halides: the role of non-innocent ligands

“…The importance of choosing an appropriate ligand is not only for better stabilization but also because beryllium compounds can activate bonds 23–25 and fixate small molecules. 26 Therefore, taking advantage of the preference of Be to form bonds with halogens, we also aimed to tackle an environmental problem due to the use of phenyl halides (which are toxic, carcinogenic, and mutagenic).…”