Next Article in Journal
First-Principles View on Photoelectrochemistry: Water-Splitting as Case Study
Next Article in Special Issue
[Bis(Trimethylsilyl)Methyl]Lithium and -Sodium: Solubility in Alkanes and Complexes with O- and N- Donor Ligands
Previous Article in Journal
Product Selectivity in Homogeneous Artificial Photosynthesis Using [(bpy)Rh(Cp*)X]n+-Based Catalysts
Previous Article in Special Issue
Hetero- and Homoleptic Magnesium Triazenides
Article Menu
Issue 2 (June) cover image

Export Article

Open AccessArticle
Inorganics 2017, 5(2), 36; doi:10.3390/inorganics5020036

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
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)
View Full-Text   |   Download PDF [2792 KB, uploaded 27 May 2017]   |  

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-(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
Figures

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Supplementary material

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

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.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Inorganics EISSN 2304-6740 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top