Oxidative addition of hexachlorodisilane to two-coordinate and formally divalent phosphorus atom

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

doi:10.1134/s0012500815060063

Cited by 17 publications

(6 citation statements)

References 8 publications

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“…Indeed, most of the chemical properties of a DDP can be explained by considering it as stabilized singlet phosphinidene, possessing nucleophilic properties. Oxidative addition to the phosphorus atom − of DDP proceeds very easily (Scheme ), whereas for the usual aromatic azaphospholes such reactions are unknown.…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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

et al. 2020

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“…In particular, hexachlorodisilane adds to the dicoordinated phosphorus atom at −30 °C with Si–Si bond cleavage to form a bis(trichlorosilyl) derivative (Scheme ). DDP reacts with halocarbons, providing 1,1-addition products without a P III → P V transition, , whereas addition reactions to the phosphorus atom for the usual aromatic azaphospholes are unknown.…”

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

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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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“…Also, DDP easily reacts with hexachlorodisilane by way of the Si–Si bond cleavage to give the 1,1‐addition product (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.

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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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Oxidative addition of hexachlorodisilane to two-coordinate and formally divalent phosphorus atom

Cited by 17 publications

References 8 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

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

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Oxidative addition of hexachlorodisilane to two-coordinate and formally divalent phosphorus atom

Cited by 17 publications

References 8 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

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

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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