Advances in beryllium coordination chemistry

Perera, Lakshika C.; Raymond, Onyekachi; Henderson, William; Plieger, Paul G.

doi:10.1016/j.ccr.2017.09.009

Cited by 93 publications

(59 citation statements)

References 213 publications

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“…As such, chemists routinely employ synthetic strategies to decorate Ae-O bonds with various aryl or alkyl functionalities and/or bulky ligands to impart both stability and solubility. Even under these strict conditions, Ae-O moieties have a propensity to form insoluble polymeric structures, particularly after loss of stabilizing ligands [3,4]. Consequently, the literature contains a relatively small number of structurally characterized compounds containing Ae-O fragments beyond weakly bound Ae<-O dative interactions resulting from coordination of ethereal solvents [5][6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

“…Herein, we report the synthesis of (sIPr) 2 BeCl 2 (1), which was used to access molecular aryloxides and alkoxides of beryllium, [(sIPr)Be(OEt)Cl] 2 (2) and (sIPr)Be(ODipp) 2 (3). In addition, we have prepared related magnesium alkoxide dimers, [(sIPr)Mg(OEt)Brl] 2 (4) and [(sIPr)Mg(OEt)Me] 2 (5). In nearly all of these cases, the synthetic route began with the preparation of a ligand stabilized metal halide complexes of Be or Mg, of which a number of examples are known [47,48].…”

Section: Introductionmentioning

confidence: 99%

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N-Heterocyclic Carbene-Supported Aryl- and Alk- oxides of Beryllium and Magnesium

et al. 2019

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Recently, we have witnessed significant progress with regard to the synthesis of molecular alkaline earth metal reagents and catalysts. To provide new precursors for light alkaline earth metal chemistry, molecular aryloxide and alkoxide complexes of beryllium and magnesium are reported. The reaction of beryllium chloride dietherate with two equivalents of 1,3-diisopropyl-4,5-dimethylimidizol-2-ylidine (sIPr) results in the formation of a bis(N-heterocyclic carbene) (NHC) beryllium dichloride complex, (sIPr)2BeCl2 (1). Compound 1 reacts with lithium diisopropylphenoxide (LiODipp) or sodium ethoxide (NaOEt) to form the terminal aryloxide (sIPr)Be(ODipp)2 (2) and alkoxide dimer [(sIPr)Be(OEt)Cl]2 (3), respectively. Compounds 2 and 3 represent the first beryllium alkoxide and aryloxide species supported by NHCs. Structurally related dimers of magnesium, [(sIPr)Mg(OEt)Brl]2 (4) and [(sIPr)Mg(OEt)Me]2 (5), were also prepared. Compounds 1-5 were characterized by single crystal X-ray diffraction studies, 1H, 13C, and 9Be NMR spectroscopy where applicable.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

N-Heterocyclic Carbene-Supported Aryl- and Alk- oxides of Beryllium and Magnesium

et al. 2019

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“…[24] Recent experimental and theoretical studies have provided evidence for the rich and versatile chemistry of beryllium. [25][26][27][28][29][30] Owing to its relatively high electronegativity and small atomic radius,the beryllium atom has the tendency to form covalent bonds with other elements,u nlike the heavier alkaline-earth metals.T he structure,b onding,a nd reactivity of simple beryllium compounds serve as excellent model systems in achieving at horough understanding of beryllium chemistry.…”

Section: Introductionmentioning

confidence: 99%

Side‐On Bonded Beryllium Dinitrogen Complexes

et al. 2020

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The preparation and spectroscopic identification of the complexes NNBe(η2‐N2) and (NN)2Be(η2‐N2) and the energetically higher lying isomers Be(NN)2 and Be(NN)3 are reported. NNBe(η2‐N2) and (NN)2Be(η2‐N2) are the first examples of covalently side‐on bonded N2 adducts of a main‐group element. The analysis of the electronic structure using modern methods of quantum chemistry suggests that NNBe(η2‐N2) and (NN)2Be(η2‐N2) should be classified as π complexes rather than metalladiazirines.

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“…Our groups are interested in all aspects of beryllium chemistry, including the design, synthesis, and characterization of strong selective ligands for beryllium coordination. [28][29][30][31][32] Here we present the serendipitous formation of a dinuclear boron compound, in which one boron atom is three-and the other is four-coordinated, and its use as a ligand in beryllium coordination chemistry. The isolated beryllium complex acts as a molecular model system for beryllium-based OLED materials as well as beryllium borates.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a Boronic Acid Anhydride Based Ligand and Its Application in Beryllium Coordination

et al. 2019

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The synthesis of a boronic acid anhydride‐based ligand containing one three‐ and one four‐coordinated boron atom is presented. This ligand was successfully employed as a tridentate κ1N,κ2O‐ligand in the coordination of beryllium chloride and both the ligand and the resulting complex have been structurally characterized. While the boron‐element separations are within the typical range of related homo‐nuclear compounds, the corresponding beryllium‐element distances are rather long, suggesting unexpectedly high electron density at the beryllium center. Incorporation of a beryllium atom in a six‐membered ring causes no more distortion than the corresponding boron atom, suggesting that analogous ligand systems could be used in boron and beryllium coordination chemistry. The generated hetero‐tri‐nuclear complex enables the direct comparison of bond lengths and angles at beryllium and boron atoms in similar coordination environments and can act as a monomolecular model for beryllium borates.

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Advances in beryllium coordination chemistry

Cited by 93 publications

References 213 publications

N-Heterocyclic Carbene-Supported Aryl- and Alk- oxides of Beryllium and Magnesium

N-Heterocyclic Carbene-Supported Aryl- and Alk- oxides of Beryllium and Magnesium

Side‐On Bonded Beryllium Dinitrogen Complexes

Synthesis of a Boronic Acid Anhydride Based Ligand and Its Application in Beryllium Coordination

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