The Reaction of Cyclohexanone Azine with PCl<sub>3</sub>. Synthesis of Annulated Dichlorodiazaphosphole and its Unusual Transannulation

Kornev, A. N.; Gorak, Olga Y.; Lukoyanova, Olga V.; Sushev, Vyacheslav V.; Panova, Yu. S.; Баранов, Е. В.; Fukin, Georgy K.; Ketkov, Sergey Yu.; Abakumov, G. A.

doi:10.1002/zaac.201200042

Cited by 13 publications

(9 citation statements)

References 30 publications

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“…While the related dichloro derivative 5 has a single resonance in the 31 P NMR spectrum, the spectrum of 4 does not appear at room temperature. Cooling the solution of 4 to −40 °C leads to the appearance of three singlets (see NMR spectra in Supporting Information).…”

Section: Resultsmentioning

confidence: 97%

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The Nature of P(σ²λ³↔σ²λ¹) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

et al. 2019

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The current study provides a clear understanding of the chemical properties of annelated 3a,6a-diaza-1,4-diphosphapentalenes (DDPs), which are best viewed as stabilized singlet phosphinidenes. It was found that DDPs undergo reversible oligomerization in solution, which provides 1,2,3-diazaphosphole-substituted cyclotetraphosphines, isolated and characterized by X-ray crystal structure analysis. Transformation of the 10-π-electron heteropentalene system into a stabilized phosphinidene occurs when the P–N bond is lengthened, which is facilitated by weak Lewis acids and bases. DFT calculations show that the lowest unoccupied molecular orbital of DDP has a high localization at the phosphorus atom when the N–P bond distance reaches the value of 2.53 Å. Oligomerization is a concentration-dependent process. Increasing the concentration of the monomer solution promotes tetramer formation, and vice versa: a strong dilution leads to a monomer. Tetramer solutions are photosensitive and yield monomers upon irradiation. The new annelated DDP 2 and its dichloro precursor 4 based on tetralone azine were synthesized. 4 exists in the solid state as a 1,4-dichloro isomer, while in solution it gives an equilibrium mixture of 1,1- and 1,4-isomers. Cyclohexanone-annelated diazadiphosphapentalene 1 forms a weak complex (1:1) with Ph3B, showing an elongated P–B bond (2.114(12) Å), which is noticeably larger than the sum of the covalent radii of the elements.

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Section: Resultsmentioning

confidence: 97%

“…The signal at 114.7 ppm is in the region characteristic of a 1,4-isomer. 33 The single resonance at 218.9 ppm is typical for the two-coordinated P atom of diazaphospholes, while the third singlet (120.9 ppm) can be attributed to the PCl 2 group of 4b (Scheme 10).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

The Nature of P(σ²λ³↔σ²λ¹) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

et al. 2019

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“…Yield of 4 remains at near the same level when an excess of hexachlorocyclopentadiene was used. In this reaction, however, dichloro‐DDP ( 7 ) was formed instead of diphosphine 5 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Synthesis of DDP(OPh) 2 (15): Diphenoxy‐DDP ( 15 ) was formed as a mixture of cis and trans isomers in the reaction of dichloro‐DDP ( 7 ) (0.32 g, 1.0 mmol in 10 mL of THF) with 2.0 mmol of PhOLi, prepared from 0.19 g of (2.0 mmol) of phenole and 2.0 mL of 1 m n BuLi in hexane. The mixture was stirred for 3 h, and filtered.…”

Section: Methodsmentioning

confidence: 99%

Structural Variability of R ₂ C Adducts of 3a,6a-Diaza-1,4-diphosphapentalene: Tuning the N→P Bonding

Kornev

Galperin

Panova

et al. 2017

Z. Anorg. Allg. Chem.

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3a,6a‐Diaza‐1,4‐diphosphapentalene (DDP) reacts with hexachlorocyclopentadiene to form a stable adduct (ClC)4C=DDP (4). The phosphorus atom involved into coordination has a pyramidal arrangement but retains partial double bonding with carbon [1.752(3) Å]. At the same time, the P–N bond remains covalent [1.824(3) Å]. The adduct 4 is better described as a zwitterionic compound with strongly delocalized positive and negative charges. A similar zwitterionic adduct DDP=C(CN)2 was prepared by the reactions of dichloro‐DDP (7) with malononitrile in the presence of Et3N. DFT calculations showed that related structures are formed in the case of the substituents (ClC)4C=, (HC)4C=, (NC)2C=, and (MeCO)2C=, possessing electron‐delocalizing properties. Compounds with other R2C groups (R = Ph, Me, C6F5, Cl), possessing electronegative properties as well, but insufficient e‐delocalization, demonstrate the noncovalent P–N bonding and a little shorter R2C–P bond lengths (ca. 1.70 Å).

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“…In the fi rst works on the synthesis of cyclohexaneannulated 1,4-dichloro-3a,6a-diaza-1,4-diphosphapentalene (1), 14 we used preliminary metallation of cyclohexanone azine with methyl lithium in diethyl ether, followed by treatment of the reaction mixture with phosphorus trichloride (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 3a,6a-diaza-1,4-diphosphapentalenes and their halogen derivatives. Specific features of the structure and behavior in solutions

et al. 2021

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Such ketazines as azines of acetophenone and its substituted derivatives (p-F, m-Cl, p-I, p-Me, p-OMe), acetone, dibenzyl ketone, propiophenone, and indan-2-one were studied in the reaction with phosphorus(III) chloride. The possibility of the formation of 1,4-dichloro-3a,6a-diaza-1,4-diphosphapentalenes is largely determined by the nature of the starting ketazine. Diazadiphosphapentalene dichlorides exist in solution as a mixture of cisand trans-isomers, but crystallize exclusively as 1,4-trans-isomers. Reduction of 3a,6a-diaza-1,4-diphosphapentalene dichlorides with manganese in tetrahydrofuran gives the corresponding diazadiphosphapentalenes in 52-63% yield. The electrochemical properties of the obtained compounds were studied by cyclic voltammetry. Two dichlorides of 3a,6a-diaza-1,4-diphosphapentalenes were found to have anomalous oxidation potentials of 0.29 and 0.13 V related to the formation of free diazadiphosphapentalenes in solution as a result of disproportionation under the infl uence of the donor solvent, which was confi rmed by 31 P NMR spectroscopy, electronic absorption spectroscopy, and independent syntheses.

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The Reaction of Cyclohexanone Azine with PCl₃. Synthesis of Annulated Dichlorodiazaphosphole and its Unusual Transannulation

Cited by 13 publications

References 30 publications

The Nature of P(σ²λ³↔σ²λ¹) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

The Nature of P(σ²λ³↔σ²λ¹) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

Structural Variability of R ₂ C Adducts of 3a,6a-Diaza-1,4-diphosphapentalene: Tuning the N→P Bonding

Synthesis of 3a,6a-diaza-1,4-diphosphapentalenes and their halogen derivatives. Specific features of the structure and behavior in solutions

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The Reaction of Cyclohexanone Azine with PCl3. Synthesis of Annulated Dichlorodiazaphosphole and its Unusual Transannulation

Cited by 13 publications

References 30 publications

The Nature of P(σ2λ3↔σ2λ1) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

The Nature of P(σ2λ3↔σ2λ1) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

Structural Variability of R 2 C Adducts of 3a,6a-Diaza-1,4-diphosphapentalene: Tuning the N→P Bonding

Synthesis of 3a,6a-diaza-1,4-diphosphapentalenes and their halogen derivatives. Specific features of the structure and behavior in solutions

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The Reaction of Cyclohexanone Azine with PCl₃. Synthesis of Annulated Dichlorodiazaphosphole and its Unusual Transannulation

The Nature of P(σ²λ³↔σ²λ¹) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

The Nature of P(σ²λ³↔σ²λ¹) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

Structural Variability of R ₂ C Adducts of 3a,6a-Diaza-1,4-diphosphapentalene: Tuning the N→P Bonding