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Main Group Chemistry: From Synthesis to Applications—In Honor of the Great Contributions of Prof. J. Derek Woollins

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

Deadline for manuscript submissions: closed (30 April 2024) | Viewed by 18240

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Guest Editor
School of Chemistry, University of St Andrews, St Andrews, UK
Interests: main group chemistry; organophosphorus; heavier group 15 (As, Sb, Bi) organoelement compounds; radical reactions; synthesis; applications

Special Issue Information

Dear Colleagues,

Molecules is delighted to host a Special Issue in honor of Prof. J. Derek Woollins on the occasion of his retirement for his outstanding contributions to main group chemistry and synthesis in particular.

Derek’s career spans a number of universities. After completing his BSc and PhD at the University of East Anglia, Derek completed postdocs in Canada, the US, and the UK before taking a lectureship position at Imperial College, where he stayed for twelve years. Derek then moved to Loughborough University as the Chair of Inorganic Chemistry, and in 1999, he moved to a chair in St Andrews University. In St Andrews, Derek served as Head of School for eight years, and as Vice Principal for Research and Innovation for six years. In 2019, Derek moved to take a position as Provost of Khalifa University, Abu Dhabi, from which he retired in 2020.

Derek is extremely well known in the academic community, in particular the inorganic and main group community, both for his scientific contributions and for his brilliant personality. His scientific interests revolve around Group 16 and 15 chemistry, in particular S/N, Se, Te, and P chemistry. Derek’s group established Ph2P2Se4, now named Woollins reagent, as an accessible and powerful selenating reagent in a range of chemistries. Derek’s efficiency is legendary, the Web of Science (November 2020) shows Derek to have 591 publications, 12,775 citations, and an H-index of 52.

Derek’s hard-working nature, witty humor, jokes, and general ability to tell a good story about anything (from science to DIY) made him a legendary lecturer amongst students as well as an extremely valuable and likeable colleague.

We wish his ability to always see the best in people stays with Derek during his long and happy retirement!

Dr. Petr Kilián
Guest Editor

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Keywords

  • molecular science
  • synthesis
  • structural chemistry
  • main group chemistry

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Published Papers (14 papers)

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Research

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16 pages, 4944 KiB  
Article
Synthesis and Characterization of Novel Cobalt Carbonyl Phosphorus and Arsenic Clusters
by Mehdi Elsayed Moussa, Susanne Bauer, Christian Graßl, Christoph Riesinger, Gábor Balázs and Manfred Scheer
Molecules 2024, 29(9), 2025; https://doi.org/10.3390/molecules29092025 - 27 Apr 2024
Viewed by 1177
Abstract
Phosphorus- and arsenic-containing cobalt clusters are an interesting class of compounds that continue to provide new structures with captivating bonding patterns. Although the first members of this family were reported 45 years ago, the number of such species is still limited within the [...] Read more.
Phosphorus- and arsenic-containing cobalt clusters are an interesting class of compounds that continue to provide new structures with captivating bonding patterns. Although the first members of this family were reported 45 years ago, the number of such species is still limited within the broad family of transition metal complexes bearing pnictogen atoms. Herein, we present the reaction of Co2(CO)8 as a cobalt source with a number of phosphorus- and arsenic-containing compounds under variable reaction conditions. These reactions result in various known and novel cobalt phosphorus and cobalt arsenic clusters in which different nuclearity ratios between P/As and Co exist. All those clusters were characterized by X-ray structural analysis and partly by IR, 31P{1H} NMR, EI-MS and elemental analysis. This comprehensive study is the first detailed study in this field that reveals the richness of compounds that could be obtained only by modifying the ratio of used reactants and the involved reaction conditions. Full article
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18 pages, 2439 KiB  
Article
Synthesis and Structural Studies of peri-Substituted Acenaphthenes with Tertiary Phosphine and Stibine Groups
by Laurence J. Taylor, Emma E. Lawson, David B. Cordes, Kasun S. Athukorala Arachchige, Alexandra M. Z. Slawin, Brian A. Chalmers and Petr Kilian
Molecules 2024, 29(8), 1841; https://doi.org/10.3390/molecules29081841 - 18 Apr 2024
Viewed by 923
Abstract
Two mixed peri-substituted phosphine-chlorostibines, Acenap(PiPr2)(SbPhCl) and Acenap(PiPr2)(SbCl2) (Acenap = acenaphthene-5,6-diyl) reacted cleanly with Grignard reagents or nBuLi to give the corresponding tertiary phosphine-stibines Acenap(PiPr2)(SbRR’) (R, R’ = [...] Read more.
Two mixed peri-substituted phosphine-chlorostibines, Acenap(PiPr2)(SbPhCl) and Acenap(PiPr2)(SbCl2) (Acenap = acenaphthene-5,6-diyl) reacted cleanly with Grignard reagents or nBuLi to give the corresponding tertiary phosphine-stibines Acenap(PiPr2)(SbRR’) (R, R’ = Me, iPr, nBu, Ph). In addition, the Pt(II) complex of the tertiary phosphine-stibine Acenap(PiPr2)(SbPh2) as well as the Mo(0) complex of Acenap(PiPr2)(SbMePh) were synthesised and characterised. Two of the phosphine-stibines and the two metal complexes were characterised by single-crystal X-ray diffraction. The peri-substituted species act as bidentate ligands through both P and Sb atoms, forming rather short Sb-metal bonds. The tertiary phosphine-stibines display through-space J(CP) couplings between the phosphorus atom and carbon atoms bonded directly to the Sb atom of up to 40 Hz. The sequestration of the P and Sb lone pairs results in much smaller corresponding J(CP) being observed in the metal complexes. QTAIM (Quantum Theory of Atoms in Molecules) and EDA-NOCV (Energy Decomposition Analysis employing Naturalised Orbitals for Chemical Valence) computational techniques were used to provide additional insight into a weak n(P)→σ*(Sb-C) intramolecular bonding interaction (pnictogen bond) in the phosphine-stibines. Full article
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19 pages, 3487 KiB  
Article
Ligand Hydrogenation during Hydroformylation Catalysis Detected by In Situ High-Pressure Infra-Red Spectroscopic Analysis of a Rhodium/Phospholene-Phosphite Catalyst
by José A. Fuentes, Mesfin E. Janka, Aidan P. McKay, David B. Cordes, Alexandra M. Z. Slawin, Tomas Lebl and Matthew L. Clarke
Molecules 2024, 29(4), 845; https://doi.org/10.3390/molecules29040845 - 14 Feb 2024
Viewed by 1139
Abstract
Phospholane-phosphites are known to show highly unusual selectivity towards branched aldehydes in the hydroformylation of terminal alkenes. This paper describes the synthesis of hitherto unknown unsaturated phospholene borane precursors and their conversion to the corresponding phospholene-phosphites. The relative stereochemistry of one of these [...] Read more.
Phospholane-phosphites are known to show highly unusual selectivity towards branched aldehydes in the hydroformylation of terminal alkenes. This paper describes the synthesis of hitherto unknown unsaturated phospholene borane precursors and their conversion to the corresponding phospholene-phosphites. The relative stereochemistry of one of these ligands and its Pd complex was assigned with the aid of X-ray crystal structure determinations. These ligands were able to approach the level of selectivity observed for phospholane-phosphites in the rhodium-catalysed hydroformylation of propene. High-pressure infra-red (HPIR) spectroscopic monitoring of the catalyst formation revealed that whilst the catalysts showed good thermal stability with respect to fragmentation, the C=C bond in the phospholene moiety was slowly hydrogenated in the presence of rhodium and syngas. The ability of this spectroscopic tool to detect even subtle changes in structure, remotely from the carbonyl ligands, underlines the usefulness of HPIR spectroscopy in hydroformylation catalyst development. Full article
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13 pages, 3186 KiB  
Article
Thermal Rearrangement of Thiocarbonyl-Stabilised Triphenylphosphonium Ylides Leading to (Z)-1-Diphenylphosphino-2-(phenylsulfenyl)alkenes and Their Coordination Chemistry
by R. Alan Aitken, Graham Dawson, Neil S. Keddie, Helmut Kraus, Heather L. Milton, Alexandra M. Z. Slawin, Joanne Wheatley and J. Derek Woollins
Molecules 2024, 29(1), 221; https://doi.org/10.3390/molecules29010221 - 31 Dec 2023
Cited by 1 | Viewed by 1118
Abstract
While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by the extrusion of Ph3PS to give alkynes in an analogous way to their carbonyl-stabilised analogues, two examples with a hydrogen atom on the ylidic carbon are found to undergo a [...] Read more.
While thiocarbonyl-stabilised phosphonium ylides generally react upon flash vacuum pyrolysis by the extrusion of Ph3PS to give alkynes in an analogous way to their carbonyl-stabilised analogues, two examples with a hydrogen atom on the ylidic carbon are found to undergo a quite different process. The net transfer of a phenyl group from P to S gives (Z)-configured 1-diphenylphosphino-2-(phenylsulfenyl)alkenes in a novel isomerisation process via intermediate λ5-1,2-thiaphosphetes. These prove to be versatile hemilabile ligands with a total of seven complexes prepared involving five different transition metals. Four of these are characterised by X-ray diffraction with two involving the bidentate ligand forming a five-membered ring metallacycle and two with the ligand coordinating to the metal only through phosphorus. Full article
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15 pages, 3435 KiB  
Article
The Covalent Linking of Organophosphorus Heterocycles to Date Palm Wood-Derived Lignin: Hunting for New Materials with Flame-Retardant Potential
by Daniel J. Davidson, Aidan P. McKay, David B. Cordes, J. Derek Woollins and Nicholas J. Westwood
Molecules 2023, 28(23), 7885; https://doi.org/10.3390/molecules28237885 - 1 Dec 2023
Cited by 4 | Viewed by 1286
Abstract
Environmentally acceptable and renewably sourced flame retardants are in demand. Recent studies have shown that the incorporation of the biopolymer lignin into a polymer can improve its ability to form a char layer upon heating to a high temperature. Char layer formation is [...] Read more.
Environmentally acceptable and renewably sourced flame retardants are in demand. Recent studies have shown that the incorporation of the biopolymer lignin into a polymer can improve its ability to form a char layer upon heating to a high temperature. Char layer formation is a central component of flame-retardant activity. The covalent modification of lignin is an established technique that is being applied to the development of potential flame retardants. In this study, four novel modified lignins were prepared, and their char-forming abilities were assessed using thermogravimetric analysis. The lignin was obtained from date palm wood using a butanosolv pretreatment. The removal of the majority of the ester groups from this heavily acylated lignin was achieved via alkaline hydrolysis. The subsequent modification of the lignin involved the incorporation of an azide functional group and copper-catalysed azide–alkyne cycloaddition reactions. These reactions enabled novel organophosphorus heterocycles to be linked to the lignin. Our preliminary results suggest that the modified lignins had improved char-forming activity compared to the controls. 31P and HSQC NMR and small-molecule X-ray crystallography were used to analyse the prepared compounds and lignins. Full article
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29 pages, 9769 KiB  
Article
Poly(imidazolyliden-yl)borato Complexes of Tungsten: Mapping Steric vs. Electronic Features of Facially Coordinating Ligands
by Callum M. Inglis, Richard A. Manzano, Ryan M. Kirk, Manab Sharma, Madeleine D. Stewart, Lachlan J. Watson and Anthony F. Hill
Molecules 2023, 28(23), 7761; https://doi.org/10.3390/molecules28237761 - 24 Nov 2023
Cited by 1 | Viewed by 1219
Abstract
A convenient synthesis of [HB(HImMe)3](PF6)2 (ImMe = N-methylimidazolyl) is decribed. This salt serves in situ as a precursor to the tris(imidazolylidenyl)borate Li[HB(ImMe)3] pro-ligand upon deprotonation with nBuLi. Reaction with [W(≡CC6H4Me-4)(CO) [...] Read more.
A convenient synthesis of [HB(HImMe)3](PF6)2 (ImMe = N-methylimidazolyl) is decribed. This salt serves in situ as a precursor to the tris(imidazolylidenyl)borate Li[HB(ImMe)3] pro-ligand upon deprotonation with nBuLi. Reaction with [W(≡CC6H4Me-4)(CO)2(pic)2(Br)] (pic = 4-picoline) affords the carbyne complex [W(≡CC6H4Me-4)(CO)2{HB(ImMe)3}]. Interrogation of experimental and computational data for this compound allow a ranking of familiar tripodal and facially coordinating ligands according to steric (percentage buried volume) and electronic (νCO) properties. The reaction of [W(≡CC6H4Me-4)(CO)2{HB(ImMe)3}] with [AuCl(SMe2)] affords the heterobimetallic semi-bridging carbyne complex [WAu(μ-CC6H4Me-4)(CO)2(Cl){HB(ImMe)3}]. Full article
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23 pages, 1367 KiB  
Article
A Convenient One-Pot Synthesis of a Sterically Demanding Aniline from Aryllithium Using Trimethylsilyl Azide, Conversion to β-Diketimines and Synthesis of a β-Diketiminate Magnesium Hydride Complex
by Nikita Demidov, Mateus Grebogi, Connor Bourne, Aidan P. McKay, David B. Cordes and Andreas Stasch
Molecules 2023, 28(22), 7569; https://doi.org/10.3390/molecules28227569 - 13 Nov 2023
Cited by 1 | Viewed by 1737
Abstract
This work reports the one-pot synthesis of sterically demanding aniline derivatives from aryllithium species utilising trimethylsilyl azide to introduce amine functionalities and conversions to new examples of a common N,N′-chelating ligand system. The reaction of TripLi (Trip = 2,4,6-iPr3 [...] Read more.
This work reports the one-pot synthesis of sterically demanding aniline derivatives from aryllithium species utilising trimethylsilyl azide to introduce amine functionalities and conversions to new examples of a common N,N′-chelating ligand system. The reaction of TripLi (Trip = 2,4,6-iPr3-C6H2) with trimethylsilyl azide afforded the silyltriazene TripN2N(SiMe3)2 in situ, which readily reacts with methanol under dinitrogen elimination to the aniline TripNH2 in good yield. The reaction pathways and by-products of the system have been studied. The extension of this reaction to a much more sterically demanding terphenyl system suggested that TerLi (Ter = 2,6-Trip2-C6H3) slowly reacted with trimethylsilyl azide to form a silyl(terphenyl)triazenide lithium complex in situ, predominantly underwent nitrogen loss to TerN(SiMe3)Li in parallel, which afforded TerN(SiMe3)H after workup, and can be deprotected under acidic conditions to form the aniline TerNH2. TripNH2 was furthermore converted to the sterically demanding β-diketimines RTripnacnacH (=HC{RCN(Trip)}2H), with R = Me, Et and iPr, in one-pot procedures from the corresponding 1,3-diketones. The bulkiest proligand was employed to synthesise the magnesium hydride complex [{(iPrTripnacnac)MgH}2], which shows a distorted dimeric structure caused by the substituents of the sterically demanding ligand moieties. Full article
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16 pages, 3264 KiB  
Article
Formation, Characterization, and Bonding of cis- and trans-[PtCl2{Te(CH2)6}2], cis-trans-[Pt3Cl6{Te(CH2)6}4], and cis-trans-[Pt4Cl8{Te(CH2)6}4]: Experimental and DFT Study
by Marko Rodewald, J. Mikko Rautiainen, Helmar Görls, Raija Oilunkaniemi, Wolfgang Weigand and Risto S. Laitinen
Molecules 2023, 28(22), 7551; https://doi.org/10.3390/molecules28227551 - 12 Nov 2023
Viewed by 1298
Abstract
[PtCl2{Te(CH2)6}2] (1) was synthesized from the cyclic telluroether Te(CH2)6 and cis-[PtCl2(NCPh)2] in dichloromethane at room temperature under the exclusion of light. The crystal structure determination [...] Read more.
[PtCl2{Te(CH2)6}2] (1) was synthesized from the cyclic telluroether Te(CH2)6 and cis-[PtCl2(NCPh)2] in dichloromethane at room temperature under the exclusion of light. The crystal structure determination showed that in the solid state, 1 crystallizes as yellow plate-like crystals of the cis-isomer 1cis and the orange-red interwoven needles of 1trans. The crystals could be separated under the microscope. NMR experiments showed that upon dissolution of the crystals of 1cis in CDCl3, it isomerizes and forms a dynamic equilibrium with the trans-isomer 1trans that becomes the predominant species. Small amounts of cis-trans-[Pt3Cl6{Te(CH2)6}4] (2) and cis-trans-[Pt4Cl8{Te(CH2)6}4] (3) were also formed and structurally characterized. Both compounds show rare bridging telluroether ligands and two different platinum coordination environments, one exhibiting a cis-Cl/cis-Te(CH2)6 arrangement and the other a trans-Cl/trans-Te(CH2)6 arrangement. Complex 2 has an open structure with two terminal and two bridging telluroether ligands, whereas complex 3 has a cyclic structure with four Te(CH2)6 bridging ligands. The bonding and formation of the complexes have been discussed through the use of DFT calculations combined with QTAIM analysis. The recrystallization of the mixture of the 1:1 reaction from d6-DMSO afforded [PtCl2{S(O)(CD3)2}{Te(CH2)6}] (4) that could also be characterized both structurally and spectroscopically. Full article
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17 pages, 7759 KiB  
Article
Hydrogen Bonds Stabilize Chloroselenite Anions: Crystal Structure of a New Salt and Donor-Acceptor Bonding to SeO2
by René T. Boeré
Molecules 2023, 28(22), 7489; https://doi.org/10.3390/molecules28227489 - 8 Nov 2023
Cited by 2 | Viewed by 1113
Abstract
The single-crystal X-ray diffraction structure characterizing a new 4-methylbenzamidinium salt of chloroselenite [C8H11N2][ClSeO2] is reported. This is only the second crystal structure report on a ClSeO2 salt. The structure contains an extended planar [...] Read more.
The single-crystal X-ray diffraction structure characterizing a new 4-methylbenzamidinium salt of chloroselenite [C8H11N2][ClSeO2] is reported. This is only the second crystal structure report on a ClSeO2 salt. The structure contains an extended planar hydrogen bond net, including a double interaction with both O atoms of the anion (an R228 ring in Etter notation). The anion has the shortest Se–Cl distances on record for any chloroselenite ion, 2.3202(9) Å. However, the two Se–O distances are distinct at 1.629(2) and 1.645(2) Å, attributed to weak anion–anion bridging involving the oxygen with the longer bond. DFT computations at the RB3PW91-D3/aug-CC-pVTZ level of theory reproduce the short Se–Cl distance in a gas-phase optimized ion pair, but free optimization of ClSeO2 leads to an elongation of this bond. A good match to a known value for [Me4N][ClSeO2] is found, which fits to the Raman spectroscopic evidence for this long-known salt and to data measured on solutions of the anion in CH3CN. The assignment of the experimental Raman spectrum was corrected by means of the DFT-computed vibrational spectrum, confirming the strong mixing of the symmetry coordinate of the Se–Cl stretch with both ν2 and ν4 modes. Full article
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17 pages, 3755 KiB  
Article
Constrained Phosphine Chalcogenide Selenoethers Supported by peri-Substitution
by Anna E. Tarcza, Alexandra M. Z. Slawin, Cameron L. Carpenter-Warren, Michael Bühl, Petr Kilian and Brian A. Chalmers
Molecules 2023, 28(21), 7297; https://doi.org/10.3390/molecules28217297 - 27 Oct 2023
Viewed by 1067
Abstract
A series of phosphorus and selenium peri-substituted acenaphthene species with the phosphino group oxidized by O, S, and Se has been isolated and fully characterized, including by single-crystal X-ray diffraction. The P(V) and Se(II) systems showed fluxional behavior in solution due to [...] Read more.
A series of phosphorus and selenium peri-substituted acenaphthene species with the phosphino group oxidized by O, S, and Se has been isolated and fully characterized, including by single-crystal X-ray diffraction. The P(V) and Se(II) systems showed fluxional behavior in solution due to the presence of two major rotamers, as evidenced with solution NMR spectroscopy. Using Variable-Temperature NMR (VT NMR) and supported by DFT (Density Functional Theory) calculations and solid-state NMR, the major rotamers in the solid and in solution were identified. All compounds showed a loss of the through-space JPSe coupling observed in the unoxidized P(III) and Se(II) systems due to the sequestration of the lone pair of the phosphine, which has been previously identified as the major contributor to the coupling pathway. Full article
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12 pages, 3007 KiB  
Article
Synthesis and Thermal Studies of Two Phosphonium Tetrahydroxidohexaoxidopentaborate(1-) Salts: Single-Crystal XRD Characterization of [iPrPPh3][B5O6(OH)4]·3.5H2O and [MePPh3][B5O6(OH)4]·B(OH)3·0.5H2O
by Michael A. Beckett, Peter N. Horton, Michael B. Hursthouse and James L. Timmis
Molecules 2023, 28(19), 6867; https://doi.org/10.3390/molecules28196867 - 29 Sep 2023
Cited by 2 | Viewed by 1030
Abstract
Two substituted phosphonium tetrahydoxidohexaoxidopentaborate(1-) salts, [iPrPPh3][B5O6(OH)4]·3.5H2O (1) and [MePPh3][B5O6(OH)4]·B(OH)3·0.5H2O (2), were prepared by templated self-assembly [...] Read more.
Two substituted phosphonium tetrahydoxidohexaoxidopentaborate(1-) salts, [iPrPPh3][B5O6(OH)4]·3.5H2O (1) and [MePPh3][B5O6(OH)4]·B(OH)3·0.5H2O (2), were prepared by templated self-assembly processes with good yields by crystallization from basic methanolic aqueous solutions primed with B(OH)3 and the appropriate phosphonium cation. Salts 1 and 2 were characterized by spectroscopic (NMR and IR) and thermal (TGA/DSC) analysis. Salts 1 and 2 were thermally decomposed in air at 800 °C to glassy solids via the anhydrous phosphonium polyborates that are formed at lower temperatures (<300 °C). BET analysis of the anhydrous and pyrolysed materials indicated they were non-porous with surface areas of 0.2–2.75 m2/g. Rhe recrystallization of 1 and 2 from aqueous solution afforded crystals suitable for single-crystal XRD analyses. The structure of 1 comprises alternating cationic/anionic layers with the H2O/pentaborate(1-) planes held together by H-bonds. The cationic planes have offset face-to-face (off) and vertex-to-face (vf) aromatic ring interactions with the iPr groups oriented towards the pentaborate(1-)/H2O layers. The anionic lattice in 2 is expanded by the inclusion of B(OH)3 molecules to accommodate the large cations; this results in the formation of a stacked pentaborate(1-)/B(OH)3 structure with channels occupied by the cations. The cations within the channels have vf, ef (edge-to-face), and off phenyl embraces. Both H-bonding and phenyl embrace interactions are important in stabilizing these two solid-state structures. Full article
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11 pages, 1640 KiB  
Article
Access to Enantiomerically Pure P-Chiral 1-Phosphanorbornane Silyl Ethers
by Kyzgaldak Ramazanova, Soumyadeep Chakrabortty, Fabian Kallmeier, Nadja Kretzschmar, Sergey Tin, Peter Lönnecke, Johannes G. de Vries and Evamarie Hey-Hawkins
Molecules 2023, 28(17), 6210; https://doi.org/10.3390/molecules28176210 - 23 Aug 2023
Cited by 3 | Viewed by 1251
Abstract
Sulfur-protected enantiopure P-chiral 1-phosphanorbornane silyl ethers 5a,b are obtained in high yields via the reaction of the hydroxy group of P-chiral 1-phosphanorbornane alcohol 4 with tert-butyldimethylsilyl chloride (TBDMSCl) and triphenylsilyl chloride (TPSCl). The corresponding optically pure silyl ethers [...] Read more.
Sulfur-protected enantiopure P-chiral 1-phosphanorbornane silyl ethers 5a,b are obtained in high yields via the reaction of the hydroxy group of P-chiral 1-phosphanorbornane alcohol 4 with tert-butyldimethylsilyl chloride (TBDMSCl) and triphenylsilyl chloride (TPSCl). The corresponding optically pure silyl ethers 5a,b are purified via crystallization and fully structurally characterized. Desulfurization with excess Raney nickel gives access to bulky monodentate enantiopure phosphorus(III) 1-phosphanorbornane silyl ethers 6a,b which are subsequently applied as ligands in iridium-catalyzed asymmetric hydrogenation of a prochiral ketone and enamide. Better activity and selectivity were observed in the latter case. Full article
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21 pages, 7180 KiB  
Article
Structures and Spectroscopic Properties of Polysulfide Radical Anions: A Theoretical Perspective
by Tristram Chivers and Richard T. Oakley
Molecules 2023, 28(15), 5654; https://doi.org/10.3390/molecules28155654 - 26 Jul 2023
Cited by 5 | Viewed by 1756
Abstract
The potential involvement of polysulfide radical anions Sn•− is a recurring theme in discussions of the basic and applied chemistry of elemental sulfur. However, while the spectroscopic features for n = 2 and 3 are well-established, information on the structures and [...] Read more.
The potential involvement of polysulfide radical anions Sn•− is a recurring theme in discussions of the basic and applied chemistry of elemental sulfur. However, while the spectroscopic features for n = 2 and 3 are well-established, information on the structures and optical characteristics of the larger congeners (n = 4–8) is sparse. To aid identification of these ephemeral species we have performed PCM-corrected DFT calculations to establish the preferred geometries for Sn•− (n = 4–8) in the polar media in which they are typically generated. TD-DFT calculations were then used to determine the number, nature and energies of the electronic excitations possible for these species. Numerical reliability of the approach was tested by comparison of the predicted and experimental excitation energies found for S2•− and S3•−. The low-energy (near-IR) transitions found for the two acyclic isomers of S4•− (C2h and C2v symmetry) and for S5•− (Cs symmetry) can be understood by extension of the simple HMO π-only chain model that serves for S2•− and S3•−. By contrast, the excitations predicted for the quasi-cyclic structures Sn•− (n = 6–8) are better described in terms of σσ* processes within a localized 2c-3e manifold. Full article
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Review

Jump to: Research

26 pages, 7977 KiB  
Review
Monofluorophos–Metal Complexes: Ripe for Future Discoveries in Homogeneous Catalysis
by Alexandra M. Miles-Hobbs, Paul G. Pringle, J. Derek Woollins and Daniel Good
Molecules 2024, 29(10), 2368; https://doi.org/10.3390/molecules29102368 - 17 May 2024
Cited by 1 | Viewed by 680
Abstract
The discovery that cyclic (ArO)2PF can support Rh-catalysts for hydroformylation with significant advantages in tuning regioselectivity transformed the study of metal complexes of monofluorophos ligands from one of primarily academic interest to one with potentially important applications in catalysis. In this [...] Read more.
The discovery that cyclic (ArO)2PF can support Rh-catalysts for hydroformylation with significant advantages in tuning regioselectivity transformed the study of metal complexes of monofluorophos ligands from one of primarily academic interest to one with potentially important applications in catalysis. In this review, the syntheses of monofluorophosphites, (RO)2PF, and monofluorophosphines, R2PF, are discussed and the factors that control the kinetic stability of these ligands to hydrolysis and disproportionation are set out. A survey of the coordination chemistry of these two classes of monofluorophos ligands with d-block metals is presented, emphasising the bonding of the fluorophos to d-block metals, predominantly in low oxidation states. The application of monofluorophos ligands in homogeneous catalysis (especially hydroformylation and hydrocyanation) is discussed, and it is argued that there is great potential for monofluorophos complexes in future catalytic applications. Full article
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