3a,6a-Diaza-1,4-Diphosphapentalene Complexes with Lewis Acids InI3 and SbCl3

Kornev, A. N.; Panova, Yu. S.; Sushev, Vyacheslav V.; Galperin, V. E.; Sheyanova, A. V.; Fukin, Georgy K.; Баранов, Е. В.; Абакумов, Г. А.

doi:10.1134/s1070328420020050

Cited by 10 publications

(5 citation statements)

References 12 publications

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“…The heteroaromatic 10-π-electron system provides two electrons for P → M bond formation, whereas the phosphorus lone pairs are not involved in the coordination. 13,21,22 T h i s c o n t e n t i s We needed to discover how DDP would react with compounds having a π-acceptor system.…”

Section: ■ Introductionsupporting

confidence: 68%

“…Meanwhile, DDP possesses a high coordination activity with metal ions and Lewis acids, being caused by a novel type of complexation (Scheme ). The heteroaromatic 10-π-electron system provides two electrons for P → M bond formation, whereas the phosphorus lone pairs are not involved in the coordination. ,, …”

Section: Introductionmentioning

confidence: 99%

“…Cyano and chloro groups in the dichlorophthalonitrile block of compound 6 are disordered with populations of ∼67% and ∼33% on C(22) and ∼33% and ∼67% on C(23) atoms, respectively. CCDC 1966779(2), 1966780 (4), 1966781(5), 1966782 (5′), and 1966783 (6) contain the supplementary crystallographic data.…”

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confidence: 99%

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Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

et al. 2020

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Herein, we present the synthesis, single-crystal X-ray structures, and spectroscopic properties for the 1:1 donor−acceptor complexes of 1,2,4,5-tetracyanobenzene (TCNB) with annelated 3a,6a-diaza-1,4-diphosphapentalenes (DDPs) based on cyclohexanone azine (2) and tetralone azine (4). These are the first complexes of an organic π-acceptor with donor phosphorus heterocycles. According to the X-ray study, the DDPs and TCNB molecules are alternately stacked with interplanar distances of 3.335 and 3.404 Å for 2 and 4, respectively, which are suitable for intermolecular π•••π interactions. The bond lengths and angles in the component molecules agree with values for neutral species, and the infrared spectra indicate a very slight degree of ionicity. The estimated HOMO−LUMO gap from the onset of optical absorption (1.40 eV) is in agreement with the band gap estimated from the density functional theory calculations for 2 (1.47 eV). By contrast, in a reaction with the related electron acceptor, tetrachloroterephthalonitrile, the DDPs proved to be donors of lone electron pairs in a nucleophilic aromatic substitution reaction of chlorine atoms demonstrating the duality of their electronic nature.

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Section: ■ Introductionsupporting

confidence: 68%

Section: Introductionmentioning

confidence: 99%

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Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

et al. 2020

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“…The first type includes reactions of the heterocyclic system (formation of πcomplexes with organic π-acceptors, [18] cycloaddition reactions, [21] rearrangement of DDP framework [22] ). The second type are reactions of stabilized singlet phosphinidene (oligomerization, [20] complexation with metal salts and Lewis acids, [23,24] oxidative addition reactions, [25][26][27][28] formation of adducts with carbenes. [29,30] The formation of two-deck dicationic compounds (DDP) 2 X 2 can be attributed to the chemical properties of DDPs of the first type, when they manifest themselves as heterocyclic systems.…”

Section: Introductionmentioning

confidence: 99%

“…The first type includes reactions of the heterocyclic system (formation of π‐complexes with organic π‐acceptors, [18] cycloaddition reactions, [21] rearrangement of DDP framework [22] ). The second type are reactions of stabilized singlet phosphinidene (oligomerization, [20] complexation with metal salts and Lewis acids, [23,24] oxidative addition reactions, [25–28] formation of adducts with carbenes [29,30] …”

Section: Introductionmentioning

confidence: 99%

A New Class of Two‐Deck Dicationic Heteropentalenes Existing by the Balance between Interdeck Aromaticity and Covalent P−P Bonding

et al. 2023

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A number of two‐deck dicationic 3a,6a‐diaza‐1,4‐diphosphapentalenes (DDP)2X2 (X=halogen or complex ion) have been characterized. Interdeck distances P(1)⋅⋅⋅P(3) and P(2)⋅⋅⋅P(4) in crystal structures, as a rule, significantly exceed the sum of covalent radii, however they are still within the sum of van der Waals radii. The 31P NMR data indicate that phosphorus atoms are equivalent in solution even at low temperatures (233 K). Based on DFT calculations, the formation of two equivalent P−P covalent bonds (<2.4 Å) is energetically unfavorable, despite the absence of steric barriers. The total energy of the model dication as a function of the P⋅⋅⋅P separation has a minimum at the P−P distance of 2.85 Å. This distance corresponds to the highest aromaticity index in the interdeck space (NICS(1.0)=−20.72). The energy of interdeck interactions is estimated at 10–15 kcal/mol.

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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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3a,6a-Diaza-1,4-Diphosphapentalene Complexes with Lewis Acids InI3 and SbCl3

Cited by 10 publications

References 12 publications

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

Dual Reactivity of 3a,6a-Diaza-1,4-diphosphapentalene: π-Donor versus n-Donor

A New Class of Two‐Deck Dicationic Heteropentalenes Existing by the Balance between Interdeck Aromaticity and Covalent P−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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