Alkaline Earth Chemistry: Synthesis and Structures

Hanusa, Timothy P.; Bierschenk, Eric J.; Engerer, Laura K.; Martin, Katherine A.; Rightmire, Nicholas R.

doi:10.1016/b978-0-08-097774-4.00145-5

Cited by 8 publications

(2 citation statements)

References 611 publications

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“…[2,3] Although the number of compounds containing Be recorded in the Cambridge Structural Database is very limited compared to those of Mg and Al, [2] it should be emphasized that major advances have been made in the area of organometallic chemistry of Be in the recent two decades both from experimental and theoretical modeling perspective. [1,2,4] Beryllium Bonds were first defined and characterized in 2009 by Yáñez, Mó and coworkers who considered the complexes between BeX 2 (X − − H, F, Cl, OH) with different Lewis bases. [5] They underlined that although beryllium bonds are in general stronger than hydrogen bonds, they share many common features.…”

Section: Introductionmentioning

confidence: 99%

Beryllium bonding: insights from the σ- and π-hole analysis

Alikhani

2020

J Mol Model

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Beryllium bonding is actually a subclass of secondary bonding. Similar to the case of halogen bonding, the σ-and π-holes on the Be atom of the monomers give in zeroth-approximation the direction of electrophilic attack favorable to the formation of beryllium bonds. The nature of beryllium bonding is purely electrostatic so that the SAPT energy decomposition perfectly explains the relevance of the polarization-and dispersion-contribution on the formation of the beryllium bond.

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Section: Introductionmentioning

confidence: 99%

Beryllium bonding: insights from the σ- and π-hole analysis

Alikhani

2020

J Mol Model

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“…has not prevented its compounds from serving as useful benchmarks of the steric and electronic consequences of crowded metal environments [8][9][10].…”

Section: Solid-state Synthesismentioning

confidence: 99%

Symmetric Assembly of a Sterically Encumbered Allyl Complex: Mechanochemical and Solution Synthesis of the Tris(allyl)beryllate, K[BeA′3] (A′ = 1,3-(SiMe3)2C3H3)

et al. 2017

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Abstract:The ball milling of beryllium chloride with two equivalents of the potassium salt of bis(1,3-trimethylsilyl)allyl anion, K[A ] (A = [1,3-(SiMe 3 ) 2 C 3 H 3 ]), produces the tris(allyl)beryllate K[BeA' 3 ] (1) rather than the expected neutral BeA' 2 . The same product is obtained from reaction in hexanes; in contrast, although a similar reaction conducted in Et 2 O was previously shown to produce the solvated species BeA' 2 (OEt 2 ), it can produce 1 if the reaction time is extended (16 h). The tris(allyl)beryllate is fluxional in solution, and displays the strongly downfield 9 Be NMR shift expected for a three-coordinate Be center (δ22.8 ppm). A single crystal X-ray structure reveals that the three allyl ligands are bound to beryllium in an arrangement with approximate C 3 symmetry (Be-C (avg) = 1.805(10) Å), with the potassium cation engaging in cation-π interactions with the double bonds of the allyl ligands. Similar structures have previously been found in complexes of zinc and tin, i.e., M[M A 3 L] (M = Zn, M = Li, Na, K; M = Sn, M = K; L = thf). Density functional theory (DFT) calculations indicate that the observed C 3 -symmetric framework of the isolated anion ([BeA 3 ] − ) is 20 kJ·mol −1 higher in energy than a C 1 arrangement; the K + counterion evidently plays a critical role in templating the final conformation.

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Hydrido‐Komplexe des Calciums: eine neue Familie molekularer Erdalkalimetall‐Verbindungen

2018

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Die Anwendung von festem CaH2 beschränkt sich fast ausschließlich auf die Nutzung als Trockenmittel, obwohl eine katalytische Aktivität lange bekannt ist. Nach der Isolierung der ersten definierten molekularen Calciumhydrid‐Verbindung im Jahr 2006 ist die Zahl an Mitgliedern dieser neuen Verbindungsklasse im folgenden Jahrzehnt stetig gestiegen. Zwar erschwert das Schlenk‐Gleichgewicht die Isolierung dieser Verbindungen, jedoch hat die Neuartigkeit der Reaktivität, besonders bei der Aktivierung kleiner Moleküle, immer mehr Interesse geweckt. In diesem Kurzaufsatz wird umfassend über die Synthese, Struktur und Reaktivität der bis dato bekannten molekularen Calciumhydride berichtet.

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Alkaline Earth Chemistry: Synthesis and Structures

Cited by 8 publications

References 611 publications

Beryllium bonding: insights from the σ- and π-hole analysis

Beryllium bonding: insights from the σ- and π-hole analysis

Symmetric Assembly of a Sterically Encumbered Allyl Complex: Mechanochemical and Solution Synthesis of the Tris(allyl)beryllate, K[BeA′3] (A′ = 1,3-(SiMe3)2C3H3)

Hydrido‐Komplexe des Calciums: eine neue Familie molekularer Erdalkalimetall‐Verbindungen

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