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Special Issue "Main Group Elements in Synthesis"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: 31 October 2018

Special Issue Editor

Guest Editor
Prof. Dr. J. Derek Woollins

Department of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
Website | E-Mail
Interests: synthesis; p block chemistry; phosphorus; sulphur; selenium; tellurium; structural science

Special Issue Information

Dear Colleagues,

Main group chemistry continues to flourish. Apart from the beauty of many main group compounds the range and application of main group systems includes, e.g., valuable reagents for organic transformations, new catalysts, potential hydrogen storage materials and new electronic materials. I am delighted to have been invited to Guest Edit a Special Issue on main group elements in synthesis. I do hope you will consider submitting an article to Molecules one of the premier open access journals. I welcome articles in the broadest sense both p-block and s-block chemistry

Prof. Dr. J. Derek Woollins
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • main group
  • p-block
  • s-block
  • transformation
  • synthesis
  • materials
  • catalysis

Published Papers (4 papers)

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Research

Open AccessArticle Diverse Derivatives of Selenoureas: A Synthetic and Single Crystal Structural Study
Molecules 2018, 23(9), 2143; https://doi.org/10.3390/molecules23092143
Received: 13 July 2018 / Revised: 20 August 2018 / Accepted: 24 August 2018 / Published: 25 August 2018
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Abstract
Reacting aroyl chlorides with an equivalent of potassium selenocyanate, followed by treating with an equivalent of 1,2,4-tri-tert-butylaniline at room temperature, resulted in the expected selenoureas and unusual diselenazoles. The selenation of selenourea by Woollins Reagent gave a new selenoformamide. Nucleophilic addition of selenoureas
[...] Read more.
Reacting aroyl chlorides with an equivalent of potassium selenocyanate, followed by treating with an equivalent of 1,2,4-tri-tert-butylaniline at room temperature, resulted in the expected selenoureas and unusual diselenazoles. The selenation of selenourea by Woollins Reagent gave a new selenoformamide. Nucleophilic addition of selenoureas with acyl bromides led to the formation of new carbamimidoselenoates rather than the expected 1,3-selenazoles. The novel compounds prepared were characterised spectroscopically and crystallographically. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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Graphical abstract

Open AccessArticle Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes
Molecules 2018, 23(5), 1138; https://doi.org/10.3390/molecules23051138
Received: 10 April 2018 / Revised: 3 May 2018 / Accepted: 4 May 2018 / Published: 10 May 2018
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Abstract
Alkali metal amides are vital reagents in synthetic chemistry and the bis(silyl)amide {N(SiMe3)2} (N′′) is one of the most widely-utilized examples. Given that N′′ has provided landmark complexes, we have investigated synthetic routes to lithium and sodium bis(silyl)amides with
[...] Read more.
Alkali metal amides are vital reagents in synthetic chemistry and the bis(silyl)amide {N(SiMe3)2} (N′′) is one of the most widely-utilized examples. Given that N′′ has provided landmark complexes, we have investigated synthetic routes to lithium and sodium bis(silyl)amides with increased steric bulk to analyse the effects of R-group substitution on structural features. To perform this study, the bulky bis(silyl)amines {HN(SitBuMe2)(SiMe3)}, {HN(SiiPr3)(SiMe3)}, {HN(SitBuMe2)2}, {HN(SiiPr3)(SitBuMe2)} and {HN(SiiPr3)2} (1) were prepared by literature procedures as colourless oils; on one occasion crystals of 1 were obtained. These were treated separately with nBuLi to afford the respective lithium bis(silyl)amides [Li{μ-N(SitBuMe2)(SiMe3)}]2 (2), [Li{μ-N(SiiPr3)(SiMe3)}]2 (3), [Li{N(SitBuMe2)2}{μ-N(SitBuMe2)2}Li(THF)] (4), [Li{N(SiiPr3)(SitBuMe2)}(DME)] (6) and [Li{N(SiiPr3)2}(THF)] (7) following workup and recrystallization. On one occasion during the synthesis of 4 several crystals of the ‘ate’ complex [Li2{μ-N(SitBuMe2)2}(μ-nBu)]2 (5) formed and a trace amount of [Li{N(SiiPr3)2}(THF)2] (8) was identified during the recrystallization of 7. The reaction of {HN(SitBuMe2)2} with NaH in the presence of 2 mol % of NaOtBu gave crystals of [Na{μ-N(SitBuMe2)2}(THF)]2 (9-THF), whilst [Na{N(SiiPr3)2}(C7H8)] (10) was prepared by deprotonation of 1 with nBuNa. The solid-state structures of 110 were determined by single crystal X-ray crystallography, whilst 24, 7, 9 and 10 were additionally characterized by NMR and FTIR spectroscopy and elemental microanalysis. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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Open AccessArticle LiGe(SiMe3)3: A New Substituent for the Synthesis of Metalloid Tin Clusters from Metastable Sn(I) Halide Solutions
Molecules 2018, 23(5), 1022; https://doi.org/10.3390/molecules23051022
Received: 28 March 2018 / Revised: 23 April 2018 / Accepted: 23 April 2018 / Published: 26 April 2018
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Abstract
The most fruitful synthetic route to metalloid tin clusters applies the disproportionation reaction of metastable Sn(I) halide solutions, whereby Si(SiMe3)3 is mostly used as the stabilizing substituent. Here, we describe the synthesis and application of the slightly modified substituent Ge(SiMe
[...] Read more.
The most fruitful synthetic route to metalloid tin clusters applies the disproportionation reaction of metastable Sn(I) halide solutions, whereby Si(SiMe3)3 is mostly used as the stabilizing substituent. Here, we describe the synthesis and application of the slightly modified substituent Ge(SiMe3)3, which can be used for the synthesis of metalloid tin clusters to give the neutral cluster Sn10[Ge(SiMe3)3]6 as well as the charged clusters {Sn10[Ge(SiMe3)3]5} and {Sn10[Ge(SiMe3)3]4}2−. The obtained metalloid clusters are structurally similar to their Si(SiMe3)3 derivatives. However, differences with respect to the stability in solution are observed. Additionally, a different electronic situation for the tin atoms is realized as shown by 119mSn Mössbauer spectroscopy, giving further insight into the different kinds of tin atoms within the metalloid cluster {Sn10[Ge(SiMe3)3]4}2−. The synthesis of diverse derivatives gives the opportunity to check the influence of the substituent for further investigations of metalloid tin cluster compounds. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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Graphical abstract

Open AccessFeature PaperArticle Phosphorus-Sulfur Heterocycles Incorporating an O-P(S)-O or O-P(S)-S-S-P(S)-O Scaffold: One-Pot Synthesis and Crystal Structure Study
Molecules 2017, 22(10), 1687; https://doi.org/10.3390/molecules22101687
Received: 7 September 2017 / Accepted: 4 October 2017 / Published: 10 October 2017
Cited by 1 | PDF Full-text (3211 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A new one-pot preparative route was developed to synthesize novel organophosphorus-sulfur heterocycles via the reaction of the four-membered ring thionation reagent [2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide (FcLR, a ferrocene analogue of Lawesson’s reagent)] and alkenyl/aryl-diols and I2 (or SOCl2) in the presence of
[...] Read more.
A new one-pot preparative route was developed to synthesize novel organophosphorus-sulfur heterocycles via the reaction of the four-membered ring thionation reagent [2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide (FcLR, a ferrocene analogue of Lawesson’s reagent)] and alkenyl/aryl-diols and I2 (or SOCl2) in the presence of triethylamine. Therefore, a series of five- to ten-membered heterocycles bearing an O-P(S)-O or an O-P(S)-S-S-P(S)-O linkage were synthesized. The synthesis features a novel application of the multicomponent reaction, providing an efficient and environmentally benign method for the preparation of the unusual phosphorus-sulfur heterocycles. Seven representative X-ray structures confirm the formation of these heterocycles. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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