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Open AccessArticle

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)

1
Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA
2
Department of Chemistry, University of Rochester, Rochester, NY 14627, USA
*
Author to whom correspondence should be addressed.
Academic Editor: Matthias Westerhausen
Inorganics 2017, 5(2), 36; https://doi.org/10.3390/inorganics5020036
Received: 23 April 2017 / Revised: 22 May 2017 / Accepted: 23 May 2017 / Published: 27 May 2017
(This article belongs to the Special Issue s-Block Metal Complexes)
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-(SiMe3)2C3H3]), 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 Et2O was previously shown to produce the solvated species BeA’2(OEt2), 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 9Be 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 C3 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′3L] (M′ = Zn, M = Li, Na, K; M′ = Sn, M = K; L = thf). Density functional theory (DFT) calculations indicate that the observed C3-symmetric framework of the isolated anion ([BeA′3]) is 20 kJ·mol−1 higher in energy than a C1 arrangement; the K+ counterion evidently plays a critical role in templating the final conformation. View Full-Text
Keywords: allyl ligands; beryllium; coordination modes; mechanochemistry; X-ray diffraction; density functional theory calculations allyl ligands; beryllium; coordination modes; mechanochemistry; X-ray diffraction; density functional theory calculations
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MDPI and ACS Style

Boyde, N.C.; Rightmire, N.R.; Hanusa, T.P.; Brennessel, W.W. 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). Inorganics 2017, 5, 36.

AMA Style

Boyde NC, Rightmire NR, Hanusa TP, Brennessel WW. 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). Inorganics. 2017; 5(2):36.

Chicago/Turabian Style

Boyde, Nicholas C.; Rightmire, Nicholas R.; Hanusa, Timothy P.; Brennessel, William W. 2017. "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)" Inorganics 5, no. 2: 36.

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