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Recent Advances in Phosphorus Chemistry
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Recent Advances in Phosphorus Chemistry

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

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 14503

Special Issue Editors

Prof. Dr. Maurizio Peruzzini

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Guest Editor
Consiglio Nazionale delle Ricerche (CNR), Istituto di Chimica dei Composti OrganoMetallici (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy
Interests: activation and functionalization of elemental phosphorus; activation of small inorganic and organic molecules; transition-metal hydrides and molecular hydrogen chemistry; materials for H-storage; carbon dioxide capture and valorization
Special Issues, Collections and Topics in MDPI journals
Dr. Maria Caporali

E-Mail Website
Guest Editor
Consiglio Nazionale delle Ricerche (CNR)-Istituto di Chimica dei Composti OrganoMetallici (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino (FI), Italy
Interests: inorganic phosphorus chemistry; homogeneous and heterogeneous catalysis with P-based compounds; metal phosphides and nanoparticles; chemistry of phosphorene
Dr. Manuel Serrano-Ruiz

E-Mail Website
Guest Editor
Consiglio Nazionale delle Ricerche (CNR) Istituto di Chimica dei Composti OrganoMetallici (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino (FI), Italy
Interests: P-ligands and complexes of transition metals with phosphines; inorganic phosphorus chemistry; organometallic polymers; homogeneous and heterogeneous catalysis; chemistry of phosphorene
Dr. Matteo Vanni

E-Mail Website
Guest Editor
Consiglio Nazionale delle Ricerche (CNR)-Istituto di Chimica dei Composti OrganoMetallici (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino (FI), Italy
Interests: phosphorus chemistry; materials chemistry; functionalization of elemental phosphorus; heterogeneous catalysis; metal nanoparticles

Special Issue Information

Dear Colleagues,

Phosphorus, the multifaceted element, is still attracting the interest of worldwide scientists and specialists from chemical industries.

This Special Issue will collect some of the most recent advances in the fascinating field of phosphorus chemistry, going from molecular science to materials and their wide applications in science and technology. It aims at focusing on the synthesis, characterization, reactivity, and applications of molecular P-based compounds in the field of inorganic, organic, and biological chemistry. Indeed, P-compounds can behave as potential ligands toward transition metals, building blocks for innovative materials and bioactive molecules with applications in life science. Understanding the reaction mechanisms will also be a target of this Special Issue. Finally, a particular focus will be given to P-based materials, including phosphides and two-dimensional materials, i.e., phosphorene, endowed with peculiar physical and chemical properties.

We invite scientists active in these broad areas of chemistry to contribute to this Special Issue with original research articles and reviews on a number of pertinent topics, including, but not limited to:

  • Activation and functionalization of elemental phosphorus;
  • Synthesis and characterization of P-based ligands and organophosphorus compounds;
  • Phosphorus-based catalysts in organic synthesis via homo- and heterogeneous processes;
  • Synthesis of bioactive phosphorus compounds and their applications;
  • Mechanistic studies by experimental methods and theoretical calculations;
  • Phosphorus-based nanomaterials (metal phosphides nanoparticles, exfoliated black phosphorus);
  • P-containing materials and their applications in energy conversion and storage.

Prof. Dr. Maurizio Peruzzini
Dr. Maria Caporali
Dr. Manuel Serrano-Ruiz
Dr. Matteo Vanni
Guest Editors

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 submissions that pass pre-check are 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 semimonthly 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 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

  • White phosphorus
  • Red phosphorus
  • Black phosphorus
  • Phosphorus ligands and complexes
  • P-based materials
  • Metal phosphides
  • Catalytic processes
  • Bioactive phosphorus compounds
  • DFT calculations
  • Surface functionalization
  • Nanomaterials

Published Papers (5 papers)

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Research

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13 pages, 2675 KiB  
Article
Insertion of Phosphenium Ions into a Bicyclo[1.1.0]Tetraphosphabutane Iron Complex
by Martin Weber, Gábor Balázs, Alexander V. Virovets, Eugenia Peresypkina and Manfred Scheer
Molecules 2021, 26(13), 3920; https://doi.org/10.3390/molecules26133920 - 26 Jun 2021
Cited by 1 | Viewed by 2268
Abstract
By reacting [{Cp‴Fe(CO)2}2(µ,η1:1-P4)] (1) with in situ generated phosphenium ions [Ph2P][A] ([A]− = [OTf]− = [O3SCF3]−, [PF6]−), a mixture [...] Read more.
By reacting [{Cp‴Fe(CO)2}2(µ,η1:1-P4)] (1) with in situ generated phosphenium ions [Ph2P][A] ([A]− = [OTf]− = [O3SCF3]−, [PF6]−), a mixture of two main products of the composition [{Cp‴Fe(CO)2}2(µ,η1:1-P5(C6H5)2)][PF6] (2a and 3a) could be identified by extensive 31P NMR spectroscopic studies at 193 K. Compound 3a was also characterized by X-ray diffraction analysis, showing the rarely observed bicyclo[2.1.0]pentaphosphapentane unit. At room temperature, the novel compound [{Cp‴Fe}(µ,η4:1-P5Ph2){Cp‴(CO)2Fe}][PF6] (4) is formed by decarbonylation. Reacting 1 with in situ generated diphenyl arsenium ions gives short-lived intermediates at 193 K which disproportionate at room temperature into tetraphenyldiarsine and [{Cp‴Fe(CO)2}4(µ4,η1:1:1:1-P8)][OTf]2 (5) containing a tetracyclo[3.3.0.02,7.03,6]octaphosphaoctane ligand. Full article
(This article belongs to the Special Issue Recent Advances in Phosphorus Chemistry)
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15 pages, 4280 KiB  
Article
C2-Symmetric P-Stereogenic Ferrocene Ligands with Heavier Chalcogenophosphinous Acid Ester Donor Sites
by Roman Franz, Clemens Bruhn and Rudolf Pietschnig
Molecules 2021, 26(7), 1899; https://doi.org/10.3390/molecules26071899 - 27 Mar 2021
Cited by 1 | Viewed by 1781
Abstract
tert-Butyl-substituted diphospha[2]ferrocenophane was used as a stereochemically confined diphosphane to investigate the addition of various dichalcoganes (R2Ch2; Ch = S, Se, Te and R = Me, Ph). Bischalcogenophosphinous acid esters bearing four soft donor sides were obtained as a mixture of rac [...] Read more.
tert-Butyl-substituted diphospha[2]ferrocenophane was used as a stereochemically confined diphosphane to investigate the addition of various dichalcoganes (R2Ch2; Ch = S, Se, Te and R = Me, Ph). Bischalcogenophosphinous acid esters bearing four soft donor sides were obtained as a mixture of rac and meso diastereomers and characterized by means of multinuclear NMR and X-ray analysis. The coordination chemistry of multidentate ligand 3b was explored toward d10 coinage metal centers (Cu(I), Ag(I), and Au(I)), yielding various bimetallic complexes. Full article
(This article belongs to the Special Issue Recent Advances in Phosphorus Chemistry)
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Review

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27 pages, 2822 KiB  
Review
The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments
by Martin B. Smith
Molecules 2022, 27(19), 6293; https://doi.org/10.3390/molecules27196293 - 23 Sep 2022
Cited by 9 | Viewed by 2278
Abstract
Organophosphorus ligands are an invaluable family of compounds that continue to underpin important roles in disciplines such as coordination chemistry and catalysis. Their success can routinely be traced back to facile tuneability thus enabling a high degree of control over, for example, electronic [...] Read more.
Organophosphorus ligands are an invaluable family of compounds that continue to underpin important roles in disciplines such as coordination chemistry and catalysis. Their success can routinely be traced back to facile tuneability thus enabling a high degree of control over, for example, electronic and steric properties. Diphosphines, phosphorus compounds bearing two separated PIII donor atoms, are also highly valued and impart their own unique features, for example excellent chelating properties upon metal complexation. In many classical ligands of this type, the backbone connectivity has been based on all carbon spacers only but there is growing interest in embedding other donor atoms such as additional nitrogen (–NH–, –NR–) sites. This review will collate some important examples of ligands in this field, illustrate their role as ligands in coordination chemistry and highlight some of their reactivities and applications. It will be shown that incorporation of a nitrogen-based group can impart unusual reactivities and important catalytic applications. Full article
(This article belongs to the Special Issue Recent Advances in Phosphorus Chemistry)
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38 pages, 17970 KiB  
Review
Recent Advances in Chemistry of Unsymmetrical Phosphorus-Based Pincer Nickel Complexes: From Design to Catalytic Applications
by Zufar N. Gafurov, Artyom O. Kantyukov, Alexey A. Kagilev, Alina A. Kagileva, Il’yas F. Sakhapov, Ilya K. Mikhailov and Dmitry G. Yakhvarov
Molecules 2021, 26(13), 4063; https://doi.org/10.3390/molecules26134063 - 02 Jul 2021
Cited by 10 | Viewed by 3677
Abstract
Pincer complexes play an important role in organometallic chemistry; in particular, their use as homogeneous catalysts for organic transformations has increased dramatically in recent years. The high catalytic activity of such bis-cyclometallic complexes is associated with the easy tunability of their properties. Moreover, [...] Read more.
Pincer complexes play an important role in organometallic chemistry; in particular, their use as homogeneous catalysts for organic transformations has increased dramatically in recent years. The high catalytic activity of such bis-cyclometallic complexes is associated with the easy tunability of their properties. Moreover, the phosphorus-based unsymmetrical pincers showed higher catalytic activity than the corresponding symmetrical analogues in several catalytic reactions. However, in modern literature, an increasing interest in the development of catalysts based on non-precious metals is observed. For example, nickel, which is an affordable and sustainable analogue of platinum and palladium, known for its low toxicity, has attracted increasing attention in the catalytic chemistry of transition metals in recent years. Thus, this mini-review is devoted to the recent advances in the chemistry of unsymmetrical phosphorus-based pincer nickel complexes, including the ligand design, the synthesis of nickel complexes and their catalytic applications. Full article
(This article belongs to the Special Issue Recent Advances in Phosphorus Chemistry)
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24 pages, 11501 KiB  
Review
AB5 Derivatives of Cyclotriphosphazene for the Synthesis of Dendrons and Their Applications
by Artem Zibarov, Abdelouahd Oukhrib, Julien Aujard Catot, Cédric-Olivier Turrin and Anne-Marie Caminade
Molecules 2021, 26(13), 4017; https://doi.org/10.3390/molecules26134017 - 30 Jun 2021
Cited by 12 | Viewed by 2934
Abstract
AB5 compounds issued from the reactivity of hexachlorocyclotriphosphazene are relatively easy to obtain using two ways: either first the reaction of one chloride with one reagent, followed by the reaction of the five remaining Cl with another reagent, or first the reaction [...] Read more.
AB5 compounds issued from the reactivity of hexachlorocyclotriphosphazene are relatively easy to obtain using two ways: either first the reaction of one chloride with one reagent, followed by the reaction of the five remaining Cl with another reagent, or first the reaction of five chlorides with one reagent, followed by the reaction of the single remaining Cl with another reagent. This particular property led to the use of such compounds as core for the synthesis of dendrons (dendritic wedges), using the five functions for growing the dendritic branches. The single function can be used for the synthesis of diverse types of dendrimers (onion peel, dumbbell-shape, Janus), for covalent or non-covalent grafting to solid surfaces, providing nanomaterials, for grafting a fluorophore, especially for studying biological mechanisms, or for self-associations to get micelles. All these properties are reviewed in this paper. Full article
(This article belongs to the Special Issue Recent Advances in Phosphorus Chemistry)
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