Adducts of dicoordinated trivalent phosphorus with carbenes

Kornev, A. N.; Galperin, V. E.; Sushev, Vyacheslav V.; Zolotareva, N. V.; Fukin, Georgy K.; Cherkasov, Anton V.; Abakumov, G. A.

doi:10.1007/s11172-016-1601-y

Cited by 14 publications

(9 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Adducts with the simplest carbenes (CCl 2 , CH 2 ) are unstable and quickly produce oligomers, 28 while carbenes with stabilizing substituents show interesting chemical properties. Recently, we have obtained the adduct of diacyl carbene with DDP, which manifested unusual dimerization with the formation of a P−P bond 29 (Scheme 6). R 2 C derivatives of DDP containing the electron delocalizing groups (ClC) 4 C and (NC) 2 C are quite stable and have a zwitterionic structure 30,31 (Scheme 7).…”

Section: ■ Introductionmentioning

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

View full text Add to dashboard Cite

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.

show abstract

Section: ■ Introductionmentioning

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

View full text Add to dashboard Cite

show abstract

“…In the recent experiments we have detected the adduct 2 of diacylcarbene with trivalent dicoordinate phosphorus of DDP, which is highly reactive and undergoes “head‐to‐head” dimerization in solution (Scheme ).…”

Section: Introductionmentioning

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.

View full text Add to dashboard Cite

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).

show abstract

“…The fi rst type includes reactions of the heterocyclic system (formation of π-complexes with organic π-acceptors, 3 cycloaddition reactions 4 ). The second type are reactions of stabilized singlet phosphinidene (oligomerization, 1 complexation with metal salts and Lewis acids, 5,6 oxidative addition reactions, 7-10 formation of adducts with carbenes 11,12 ). To date, we have described only two 3a,6a-diaza-1,4-diphosphapentalenes synthesized from azines of cyclohexanone 13 and tetralone.…”

Section: Methodsmentioning

confidence: 99%

“…2,5-Dimethyl-3,6-diphenyl-3а,6а-diaza-1,4-diphospha pentalene (11). A solution of propiophenone azine (0.23 g, 0.66 mmol) in THF (15 mL) was added to a vacuum preheated manganese powder (0.121 g, 2.2 mmol).…”

mentioning

confidence: 99%

“…Crystallographic data and the X-ray data collection and refi nement statistics for 2-6, 8, 10, and 11 are given in Tables 6 and 7. The structures were deposited with the Cambridge Crystallographic Data Center (CCDC: 2064973 (2), 2064974 (3), 2064975 (4), 2064976 (5), 2064977 (6), 2064978 (8), 2064979 (10), 2064980 (11) and are available at ccdc.cam.ac.uk/ getstructures. This work was fi nancially supported by the Russian Science Foundation (Project No.…”

mentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2021

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Adducts of dicoordinated trivalent phosphorus with carbenes

Cited by 14 publications

References 12 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

Contact Info

Product

Resources

About

Adducts of dicoordinated trivalent phosphorus with carbenes

Cited by 14 publications

References 12 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

Contact Info

Product

Resources

About

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