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Main Group Elements in Synthesis
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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: closed (31 October 2018) | Viewed by 38439

Special Issue Editor

Prof. Dr. J. Derek Woollins

E-Mail Website
Guest Editor
Department of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK
Interests: synthesis; p block chemistry; phosphorus; sulphur; selenium; tellurium; structural science; molecular main group chemistry
Special Issues, Collections and Topics in MDPI journals

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

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 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 (10 papers)

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Research

15 pages, 2675 KiB  
Article
Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties
by Heli Laasonen, Johanna Ikäheimonen, Mikko Suomela, J. Mikko Rautiainen and Risto S. Laitinen
Molecules 2019, 24(2), 319; https://doi.org/10.3390/molecules24020319 - 16 Jan 2019
Cited by 3 | Viewed by 2976
Abstract
[TiCp2S5] (phase A), [TiCp2Se5] (phase F), and five solid solutions of mixed titanocene selenide sulfides [TiCp2SexS5−x] (Cp = C5H5−) with the [...] Read more.
[TiCp2S5] (phase A), [TiCp2Se5] (phase F), and five solid solutions of mixed titanocene selenide sulfides [TiCp2SexS5−x] (Cp = C5H5−) with the initial Se:S ranging from 1:4 to 4:1 (phases B–E) were prepared by reduction of elemental sulfur or selenium or their mixtures by lithium triethylhydridoborate in thf followed by the treatment with titanocene dichloride [TiCp2Cl2]. Their 77Se and 13C NMR spectra were recorded from the CS2 solution. The definite assignment of the 77Se NMR spectra was based on the PBE0/def2-TZVPP calculations of the 77Se chemical shifts and is supported by 13C NMR spectra of the samples. The following complexes in varying ratios were identified in the CS2 solutions of the phases B–E: [TiCp2Se5] (51), [TiCp2Se4S] (41), [TiCp2Se3S2] (31), [TiCp2SSe3S] (36), [TiCp2SSe2S2] (25), [TiCp2SSeS3] (12), and [TiCp2S5] (01). The disorder scheme in the chalcogen atom positions of the phases B–E observed upon crystal structure determinations is consistent with the spectral assignment. The enthalpies of formation calculated for all twenty [TiCp2SexS5−x] (x = 0–5) at DLPNO-CCSD(T)/CBS level including corrections for core-valence correlation and scalar relativistic, as well as spin-orbit coupling contributions indicated that within a given chemical composition, the isomers of most favourable enthalpy of formation were those, which were observed by 77Se and 13C NMR spectroscopy. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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19 pages, 30765 KiB  
Article
Synthesis, Structure, Thermal Behavior and cis/trans Isomerization of 2,2′-(EMe3)2 (E = C, Si, Ge, Sn) Substituted Azobenzenes
by Jonas Hoffmann, Thomas Josef Kuczmera, Enno Lork and Anne Staubitz
Molecules 2019, 24(2), 303; https://doi.org/10.3390/molecules24020303 - 15 Jan 2019
Cited by 5 | Viewed by 4915
Abstract
The synthesis of a series of 2,2′-bis(trimethyltetrel) azobenzenes is reported, evaluating the different synthetic approaches that different group 14 element substituents individually require. The synthetic access to the carbon substituted congener is very different from the heavier tetrels, in that the key step [...] Read more.
The synthesis of a series of 2,2′-bis(trimethyltetrel) azobenzenes is reported, evaluating the different synthetic approaches that different group 14 element substituents individually require. The synthetic access to the carbon substituted congener is very different from the heavier tetrels, in that the key step is the formation of the N=N bond in azobenzene, rather than the azobenzene-C bond. Sn could be introduced with a cross-coupling route, whereas the Si and Ge congeners were prepared by a stannylation-lithiation-electrophilic quenching sequence. Iodo-lithium exchange was also a possible route to obtain the dilithiated species, which can be attributed to the chelating effect of the nitrogen atoms. However, the organo-lead species could not be obtained via these routes. The resulting structures were fully characterized (NMR, FTIR, HRMS and XRD). Furthermore, their thermal properties (TGA and DSC) and their photoswitching behavior in solution (UV-VIS & NMR experiments) were investigated and compared for the different tetrels (C, Si, Ge, Sn). Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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16 pages, 3338 KiB  
Article
Quantum Chemical Calculations on CHOP Derivatives—Spanning the Chemical Space of Phosphinidenes, Phosphaketenes, Oxaphosphirenes, and COP− Isomers
by Alicia Rey, Arturo Espinosa Ferao and Rainer Streubel
Molecules 2018, 23(12), 3341; https://doi.org/10.3390/molecules23123341 - 17 Dec 2018
Cited by 13 | Viewed by 3127
Abstract
After many decades of intense research in low-coordinate phosphorus chemistry, the advent of Na[OCP] brought new stimuli to the field of CHOP isomers and derivatives thereof. The present theoretical study at the CCSD(T)/def2-TZVPP level describes the chemical space of CHOP isomers in terms [...] Read more.
After many decades of intense research in low-coordinate phosphorus chemistry, the advent of Na[OCP] brought new stimuli to the field of CHOP isomers and derivatives thereof. The present theoretical study at the CCSD(T)/def2-TZVPP level describes the chemical space of CHOP isomers in terms of structures and potential energy surfaces, using oxaphosphirene as the starting point, but also covering substituted derivatives and COP− isomers. Bonding properties of the P–C, P–O, and C–O bonds in all neutral and anionic isomeric species are discussed on the basis of theoretical calculations using various bond strengths descriptors such as WBI and MBO, but also the Lagrangian kinetic energy density per electron as well as relaxed force constants. Ring strain energies of the superstrained 1H-oxaphosphirene and its barely strained oxaphosphirane-3-ylidene isomer were comparatively evaluated with homodesmotic and hyperhomodesmotic reactions. Furthermore, first time calculation of the ring strain energy of an anionic ring is described for the case of oxaphosphirenide. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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12 pages, 2350 KiB  
Article
Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization
by Francisco M. García-Valle, Vanessa Tabernero, Tomás Cuenca, Jesús Cano and Marta E. G. Mosquera
Molecules 2018, 23(12), 3108; https://doi.org/10.3390/molecules23123108 - 27 Nov 2018
Cited by 3 | Viewed by 2572
Abstract
New heterometallic aluminium-alkali metal compounds have been prepared using Schiff bases with electron withdrawing substituents as ligands. The synthesis of these new species was achieved via the reaction of AlMe3 with the freshly prepared alkali-metallated ligand. The derivatives formed were characterized by [...] Read more.
New heterometallic aluminium-alkali metal compounds have been prepared using Schiff bases with electron withdrawing substituents as ligands. The synthesis of these new species was achieved via the reaction of AlMe3 with the freshly prepared alkali-metallated ligand. The derivatives formed were characterized by NMR in solution and by single crystal X-ray diffraction in the solid state. Aluminate derivatives with lithium and sodium were prepared and a clear influence of the alkali metal in the final outcome is observed. The presence of a Na···F interaction in the solid state has a stabilization effect and the species [NaAlMe3L]2 can de isolated for the first time, which was not possible when using Schiff bases without electron withdrawing substituents as ligands. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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9 pages, 1465 KiB  
Article
Bis(6-Diphenylphosphinoacenaphth-5-yl)Telluride as a Ligand toward Manganese and Rhenium Carbonyls
by Truong Giang Do, Emanuel Hupf, Enno Lork and Jens Beckmann
Molecules 2018, 23(11), 2805; https://doi.org/10.3390/molecules23112805 - 29 Oct 2018
Cited by 6 | Viewed by 2773
Abstract
The reaction of the previously known bis(6-diphenylphosphinoacenaphthyl-5-)telluride (6-Ph2P-Ace-5-)2Te (IV) with (CO)5ReCl and (CO)5MnBr proceeded with the liberation of CO and provided fac-(6-Ph2P-Ace-5-)2TeM(X)(CO)3 (fac-1: [...] Read more.
The reaction of the previously known bis(6-diphenylphosphinoacenaphthyl-5-)telluride (6-Ph2P-Ace-5-)2Te (IV) with (CO)5ReCl and (CO)5MnBr proceeded with the liberation of CO and provided fac-(6-Ph2P-Ace-5-)2TeM(X)(CO)3 (fac-1: M = Re, X = Cl; fac-2: M = Mn, X = Br), in which IV acts as bidentate ligand. In solution, fac-1 and fac-2 are engaged in a reversible equilibrium with mer-(6-Ph2P-Ace-5-)2TeM(X)(CO)3 (mer-1: M = Re, X = Cl; mer-2: M = Mn, X = Br). Unlike fac-1, fac-2 is prone to release another equivalent of CO to give (6-Ph2P-Ace-5-)2TeMn(Br)(CO)2 (3), in which IV serves as tridentate ligand. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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21 pages, 2127 KiB  
Article
Safe Synthesis of 4,7-Dibromo[1,2,5]thiadiazolo[3,4-d]pyridazine and Its SNAr Reactions
by Timofey N. Chmovzh, Ekaterina A. Knyazeva, Konstantin A. Lyssenko, Vadim V. Popov and Oleg A. Rakitin
Molecules 2018, 23(10), 2576; https://doi.org/10.3390/molecules23102576 - 09 Oct 2018
Cited by 26 | Viewed by 4016
Abstract
A safe and efficient synthesis of 4,7-dibromo[1,2,5]thiadiazolo[3,4-d]pyridazine from the commercial diaminomaleonitrile is reported. Conditions for selective aromatic nucleophilic substitution of one or two bromine atoms by oxygen and nitrogen nucleophiles are found, whereas thiols formed the bis-derivatives only. Buchwald-Hartwig or Ullmann [...] Read more.
A safe and efficient synthesis of 4,7-dibromo[1,2,5]thiadiazolo[3,4-d]pyridazine from the commercial diaminomaleonitrile is reported. Conditions for selective aromatic nucleophilic substitution of one or two bromine atoms by oxygen and nitrogen nucleophiles are found, whereas thiols formed the bis-derivatives only. Buchwald-Hartwig or Ullmann techniques are successful for incorporation of a weak nitrogen base, such as carbazole, into the [1,2,5]thiadiazolo[3,4-d]pyridazine core. The formation of rather stable S…η2-(N=N) bound chains in 4,7-bis(alkylthio)-[1,2,5]thiadiazolo[3,4-d]pyridines makes these compounds promising for the design of liquid crystals. Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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15 pages, 6876 KiB  
Article
Diverse Derivatives of Selenoureas: A Synthetic and Single Crystal Structural Study
by Guoxiong Hua, David B. Cordes, Junyi Du, Alexandra M. Z. Slawin and J. Derek Woollins
Molecules 2018, 23(9), 2143; https://doi.org/10.3390/molecules23092143 - 25 Aug 2018
Cited by 8 | Viewed by 3321
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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15 pages, 4691 KiB  
Article
Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes
by Hannah M. Nicholas, Conrad A. P. Goodwin, Jon G. C. Kragskow, Selena J. Lockyer and David P. Mills
Molecules 2018, 23(5), 1138; https://doi.org/10.3390/molecules23051138 - 10 May 2018
Cited by 8 | Viewed by 4728
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 1–10 were determined by single crystal X-ray crystallography, whilst 2–4, 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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1 pages, 4327 KiB  
Article
LiGe(SiMe3)3: A New Substituent for the Synthesis of Metalloid Tin Clusters from Metastable Sn(I) Halide Solutions
by Mareike Binder, Claudio Schrenk, Theresa Block, Rainer Pöttgen and Andreas Schnepf
Molecules 2018, 23(5), 1022; https://doi.org/10.3390/molecules23051022 - 26 Apr 2018
Cited by 7 | Viewed by 4274
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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3211 KiB  
Article
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
by Guoxiong Hua, Kate Davidson, David B. Cordes, Junyi Du, Alexandra M. Z. Slawin and J. Derek Woollins
Molecules 2017, 22(10), 1687; https://doi.org/10.3390/molecules22101687 - 10 Oct 2017
Cited by 2 | Viewed by 4799
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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