Synthesis of free and ligated 1,2-thiaphosphetanes – expanding the pool of strained P-ligands

Kyri, Andreas Wolfgang; Gleim, Florian; Biskup, David; Schnakenburg, Gregor; Ferao, Arturo Espinosa; Streubel, Rainer

doi:10.1039/c8cc09892a

Cited by 7 publications

(7 citation statements)

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“…Both valence isomerization processes from oxaphosphiranes and their P complexes have been thoroughly studied for a variety of ring substituents . A breakthrough in the synthesis of oxaphosphirane complexes similar to 8 was achieved in 2007 by a low-temperature reaction of Li/Cl phosphinidenoid complexes with carbonyl compounds. , Previously, synthesis relied on a reaction of the carbonyl unit with a thermally generated terminal phosphinidene complex, through ring closure of a transient intermediate of type 1f . In some cases, different final products were obtained upon reaction of carbonyl derivatives with either phosphinidene or phosphinidenoid complexes and their formation can be explained by intermediacy of 1f -type species ,,, or involving C–O bond cleavage complexes (similar to 9 ) .…”

Section: Resultsmentioning

confidence: 99%

Terminal Phosphinidene Complex Adducts with Neutral and Anionic O-Donors and Halides and the Search for a Differentiating Bonding Descriptor

et al. 2020

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The stability and some characteristic bonding features of a variety of ligand (L)-stabilized phosphinidene complexes derived from adduct formation with halides, and both anionic or neutral O-donor bases were explored. Furthermore, the main features of L → P pnictogen bonding in such adducts were studied not only by using geometric criteria such as L–P bond distances and pyramidalization or planarity at P but also by turning the spotlight on bond-strength-related (including atoms-in-molecules-derived) parameters, thermodynamic stability dependence with electronic characteristics of the free ligand, and dative-bonding participation. We propose the new relative positions of the charge concentration band descriptor, τVSCC, which, together with the sign and magnitude of ∇2ρ at the bond critical point, constitutes the required criteria to differentiate L–P linkages as van der Waals interactions, dative bonding, or mostly covalent bonds.

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Section: Resultsmentioning

confidence: 99%

Terminal Phosphinidene Complex Adducts with Neutral and Anionic O-Donors and Halides and the Search for a Differentiating Bonding Descriptor

et al. 2020

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“…First, the two possible retro-[2 + 2] cycloaddition pathways of 1 were studied, namely, the so-called inverse Wittig cycloreversion, affording phosphaalkene ( 2 ) and thiocarbonyl components ( 3 ) which otherwise could serve as precursors, and the normal Wittig fragmentation pathway leading to ethylene ( 4 ) and P -sulfide derivatives ( 5 ) (Scheme ). In contrast to the previous short communication, the Δ G and not the Δ E ZPE values are reported here for all relative energies. In the case of σ 5 λ 5 -derivative 1e , the most stable isomer locating the H- (and not the Me) P-substituents in the axial position opposite to the ring S atom (ΔΔ G = 4.2 kcal/mol) was considered.…”

Section: Results and Discussionmentioning

confidence: 99%

“…4 Even more recently, a related study of unligated and coordinated 1,2σ 3 λ 3 -thiaphosphetanes was communicated, again including preliminary computational results on the stability of the 1,2-thiaphosphetane ring system toward retro-[2 + 2] cycloadditions. 5 Herein, the exploration of the potential energy surfaces (PESs) of fundamental representatives of 1,2-thiaphosphetanes is presented, concerning various ring-cleavage and -opening reactions and ring enlargement and contractions, including some unique examples of thiirane P-adducts that lead to desulfurization. The following derivatives have been selected for the theoretical study on the CCSD(T) level: the unligated 1,2σ 3 λ 3 -thiaphosphetane (1a), its κP-pentacarbonylmolybdenum(0) complex (1b), the P-oxide (1c), the P-sulfide (1d) and the 1,2σ 5 λ 5 -derivative of 1a bearing two (more) Pmethyl groups (1e) (Figure 1) are presented.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In addition, the theoretical exploration of the stability of some model derivatives toward different retro-[2 + 2] cycloaddition paths was described . Even more recently, a related study of unligated and coordinated 1,2σ 3 λ 3 -thiaphosphetanes was communicated, again including preliminary computational results on the stability of the 1,2-thiaphosphetane ring system toward retro-[2 + 2] cycloadditions …”

Section: Introductionmentioning

confidence: 99%

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1,2-Thiaphosphetanes: The Quest for Wittig-Type Ring Cleavage, Rearrangement, and Sulfur Atom Transfer

Ferao

Streubel

2020

Inorg. Chem.

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The potential energy surface for opening and ring-enlargement reactions of 1,2-thiaphosphetane with different oxidation states and coordination at phosphorus has been computationally explored. The most favored [2 + 2] cycloreversions are the so-called normal Wittig-type reactions furnishing an alkene and a PS-containing component. Somewhat unfavored are reactions involving the P−S bond cleavage and a C-to-P hydrogen shift as well as a ring enlargement to a 1,3,2-dithiaphospholane in the case of high coordinate derivatives. Apart from a twostep P-to-S oxygen transfer in 1,2σ 4 λ 5 -thiaphosphetane P-oxide, an interesting reaction is the P−S bond cleavage leading to a thiabetaine which, alternatively, can be formed by the C-attack of a phosphinidene oxide on a thiirane. A similar route, energetically more favored, was found for 1,2σ 5 λ 5 -thiaphosphetane starting from thiirane and the corresponding phosphane. For a wide set of P(III) reagents including HPR 2 (R = Me, Ph), PR 3 (R = Me, Ph, NMe 2 , OMe, F, Cl), and HPO, the competitive direct S-attack was found to be the preferred pathway for the desulfurization of thiiranes, and the relative tendency for these P(III) reagents to act as an S-atom acceptor, the thermodynamic S-transfer potential (TSP) scale, was defined using the S 8 /S 7 couple as a point of reference. Article pubs.acs.org/IC

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“…oxaphosphetanes and thioanalogues prepared from Witting reaction intermediate, also attract researchers due to their reactivity (Espinosa Ferao & Streubel, 2020;A. Kyri et al, 2018;A. W. Kyri et al, 2019).…”

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Theoretical Study of The Reaction of Ketene with Methanimine Using DFT Method

2021

ZJPAS

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The Density Functional Theory (DFT) method was used to investigate the stepwise mechanism of the [2+2] cycloaddition (22CA) reaction of ketene with methanimine at the B3LYP/6-311++G(d,p) level of theory. Two modes of attack between reactants were investigated, yielding Azetidin-2-one from path1 and Azetidin-2-one from path2 as two possible products passing through two different transition states. The geometry of transition states and products was analysed. The study of stationary points and energetic parameters shows that the reaction mechanism is stepwise and that Azetidin-2-one P1 is thermodynamically and kinetically more favoured than Azetidin-3-one P2. The analysis of the frontier molecular HOMO and LUMO orbitals shows that the Azetidin-2-one P1 is more stable due to its higher energy gab. The global electronic flux from the strong nucleophilic ketene R1 to the methanimine R2 is predicted using conceptual density functional theory (CDFT) indices. Reactant's electrophilic and nucleophilic Fukui functions were also investigated.

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Synthesis of free and ligated 1,2-thiaphosphetanes – expanding the pool of strained P-ligands

Abstract: The 1,2-thiaphosphetane heterocycle could be synthesized for the first time in the coordination sphere of a metal complex (I) from which the free ligand (II) could be obtained, too.

Cited by 7 publications

References 24 publications

Terminal Phosphinidene Complex Adducts with Neutral and Anionic O-Donors and Halides and the Search for a Differentiating Bonding Descriptor

Terminal Phosphinidene Complex Adducts with Neutral and Anionic O-Donors and Halides and the Search for a Differentiating Bonding Descriptor

1,2-Thiaphosphetanes: The Quest for Wittig-Type Ring Cleavage, Rearrangement, and Sulfur Atom Transfer

Theoretical Study of The Reaction of Ketene with Methanimine Using DFT Method

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