Bis(1,3‐trimethylsilylallyl)beryllium

Chmely, Stephen C.; Hanusa, Timothy P.; Brennessel, William W.

doi:10.1002/anie.201001866

Cited by 35 publications

(17 citation statements)

References 41 publications

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“…Treatment of BeCl 2 with potassium 1,3-bistrimethylsilylallyl in Et 2 Og ave the s-bound allyl-beryllium complex 34.T his compound exhibits fluxional behavior in solution and provided the first evidence for Schlenk type equilibria in beryllium organyls. [44] Salt-metathesis reactions of BeCl 2 or BeBr 2 with one equivalent of ab ulky lithium aryl in diethyl ether leads to threefold-coordinated complexes in whicho ne aryl, one halide, and one ether molecule are bound to the beryllium atom. Introduction of as terically demanding amido ligand then gives the twofold-coordinated linear compound 35.…”

Section: C-donor Ligandsmentioning

confidence: 99%

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Recent Contributions to the Coordination Chemistry of Beryllium

Buchner

2019

Chemistry A European J

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Given the alleged extreme toxicity of beryllium and its compounds, it is the least investigated nonradioactive element. However, beryllium exhibits unique properties among the elements and therefore the related coordination chemistry is unprecedented. With the emergence of s‐block catalysis and the introduction of low‐valent magnesium complexes as versatile reducing agents, the interest in related beryllium compounds also has increased. Therefore, some quite remarkable progress on the coordination and organometallic chemistry of beryllium has been made in the last two decades. This Minireview article gives an oversight over the relatively recent developments in this field of beryllium research. An emphasis is placed on the correlation between the structure and reactivity of the described compounds.

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Section: C-donor Ligandsmentioning

confidence: 99%

“…Beryllium organyls, beryllium-carbenea nd carbodiphosphorane complexes (Mes = 2,4,6-Me 3 C 6 H 2 ;dipp = 2,6-iPr 2 C 6 H 3 ). [25,26,38,39,41,44] Chem.E ur.J. 2019, 25,12018 -12036 www.chemeurj.org bond order of 1.5.…”

Section: C-donor Ligandsmentioning

confidence: 99%

Recent Contributions to the Coordination Chemistry of Beryllium

Buchner

2019

Chemistry A European J

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“…[23] These resonances are clearly different from those in the more complex spectrum of [{MgA' 2 } 2 ], which reflect monomer-Qdimer rearrangement in solution. [7] Crystals of 1 suitable for X-ray crystal diffraction were originally grown from as lowly evaporated toluene solution, and although they ultimately yielded as tructure of connectivity-only quality (Figure 3), several features are worth noting. Thec omplex is at rimetallic monomer with af undamental composition of 2:1:4K/Mg/A',which does not reflect the reagent stoichiometry.One allyl ligand is found h 1 -bonded to the Mg center.…”

Section: Resultsmentioning

confidence: 99%

“…[6] However,f or the Group 2metals,only alimited range of bonding patterns has been documented. To date,b eryllium compounds have been found with s-bound (h 1 )( Figure 1a) [7] and m 2 -h 1 ,h 2 allyls (Figure 1h). [8] In contrast, with very rare exceptions, h 3conformations are uniformly the norm with complexes of the heavier alkaline-earth metals (Ca-Ba).…”

Section: Introductionmentioning

confidence: 99%

An η³‐Bound Allyl Ligand on Magnesium in a Mechanochemically Generated Mg/K Allyl Complex

et al. 2020

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Milling two equivalents of K[1,3-(SiMe 3 ) 2 C 3 H 3 ] (= K[A']) with MgX 2 (X = Cl, Br) produces the allyl complex [K 2 MgA' 4 ](1). Crystals grown from toluene are of the solvated species [((h 6 -tol)K) 2 MgA' 4 ]([1·2(tol)]), atrimetallic monomer with both bridging and terminal (h 1 )a llyl ligands.W hen recrystallized from hexanes,t he unsolvated 1 forms a2 D coordination polymer,inwhich the Mg is surrounded by three allyl ligands.T he CÀCb ond lengths differ by only 0.028 , indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an h 3 -allyl configuration on Mg is energetically preferred over the h 1 -(sbonded) arrangement, but the Mg must be in al ow coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerizedby1,with activities that are comparable to K[A']a nd greater than the homometallic magnesium complex [{MgA' 2 } 2 ].

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“…These findings are consistent with studies that showed that for some fluxional beryllium allyl complexes, recently synthesized, both σ-and π-bound forms would be potential energy minima. 54 It is worth noting that although for BH 3 containing complexes the value of Δ r G 1 0 for the ethynyl containing systems is smaller in absolute value than for the vinyl containing analogues, in all cases the formation of the complexes is predicted to be exergonic.…”

Section: Acidity Enhancementmentioning

confidence: 90%

Acidity enhancement of unsaturated bases of group 15 by association with borane and beryllium dihydride. Unexpected boron and beryllium Brønsted acids

et al. 2015

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The intrinsic acidity of CH 2 vCHXH 2 , HCuCXH 2 (X = N, P, As, Sb) derivatives and of their complexes with BeH 2 and BH 3 has been investigated by means of high-level density functional theory and molecular orbital ab initio calculations, using as a reference the ethyl saturated analogues. The acidity of the free systems steadily increases down the group for the three series of derivatives, ethyl, vinyl and ethynyl. The association with both beryllium dihydride and borane leads to a very significant acidity enhancement, being larger for BeH 2 than for BH 3 complexes. This acidity enhancement, for the unsaturated compounds, is accompanied by a change in the acidity trends down the group, which do not steadily decrease but present a minimum value for both the vinyl-and the ethynyl-phosphine. When the molecule acting as the Lewis acid is beryllium dihydride, the π-type complexes in which the BeH 2 molecules interact with the double or triple bond are found, in some cases, to be more stable, in terms of free energies, than the conventional complexes in which the attachment takes place at the heteroatom, X. The most important finding, however, is that P, As, and Sb ethynyl complexes with BeH2 do not behave as P, As, or Sb Brønsted acids, but unexpectedly as Be acids.

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Bis(1,3‐trimethylsilylallyl)beryllium

Cited by 35 publications

References 41 publications

Recent Contributions to the Coordination Chemistry of Beryllium

Recent Contributions to the Coordination Chemistry of Beryllium

An η³‐Bound Allyl Ligand on Magnesium in a Mechanochemically Generated Mg/K Allyl Complex

Acidity enhancement of unsaturated bases of group 15 by association with borane and beryllium dihydride. Unexpected boron and beryllium Brønsted acids

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Bis(1,3‐trimethylsilylallyl)beryllium

Cited by 35 publications

References 41 publications

Recent Contributions to the Coordination Chemistry of Beryllium

Recent Contributions to the Coordination Chemistry of Beryllium

An η3‐Bound Allyl Ligand on Magnesium in a Mechanochemically Generated Mg/K Allyl Complex

Acidity enhancement of unsaturated bases of group 15 by association with borane and beryllium dihydride. Unexpected boron and beryllium Brønsted acids

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An η³‐Bound Allyl Ligand on Magnesium in a Mechanochemically Generated Mg/K Allyl Complex