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The Nature of P(σ2λ3â"σ2λ1) Dualism : 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene. / Kornev, Alexander N.; Panova, Yulia S.; Sushev, Vyacheslav V.; Dorado Daza, Diego F.; Novikov, Alexander S.; Cherkasov, Anton V.; Fukin, Georgy K.; Abakumov, Gleb A.

в: Inorganic Chemistry, Том 58, № 23, 02.12.2019, стр. 16144-16153.

Результаты исследований: Научные публикации в периодических изданияхстатьяРецензирование

Harvard

Kornev, AN, Panova, YS, Sushev, VV, Dorado Daza, DF, Novikov, AS, Cherkasov, AV, Fukin, GK & Abakumov, GA 2019, 'The Nature of P(σ2λ3â"σ2λ1) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene', Inorganic Chemistry, Том. 58, № 23, стр. 16144-16153. https://doi.org/10.1021/acs.inorgchem.9b02690

APA

Kornev, A. N., Panova, Y. S., Sushev, V. V., Dorado Daza, D. F., Novikov, A. S., Cherkasov, A. V., Fukin, G. K., & Abakumov, G. A. (2019). The Nature of P(σ2λ3â"σ2λ1) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene. Inorganic Chemistry, 58(23), 16144-16153. https://doi.org/10.1021/acs.inorgchem.9b02690

Vancouver

Kornev AN, Panova YS, Sushev VV, Dorado Daza DF, Novikov AS, Cherkasov AV и пр. The Nature of P(σ2λ3â"σ2λ1) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene. Inorganic Chemistry. 2019 Дек. 2;58(23):16144-16153. https://doi.org/10.1021/acs.inorgchem.9b02690

Author

Kornev, Alexander N. ; Panova, Yulia S. ; Sushev, Vyacheslav V. ; Dorado Daza, Diego F. ; Novikov, Alexander S. ; Cherkasov, Anton V. ; Fukin, Georgy K. ; Abakumov, Gleb A. / The Nature of P(σ2λ3â"σ2λ1) Dualism : 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene. в: Inorganic Chemistry. 2019 ; Том 58, № 23. стр. 16144-16153.

BibTeX

@article{b64f9a5b85fb4766811d6584df1634b7,
title = "The Nature of P(σ2λ3{\^a}{"}σ2λ1) Dualism: 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene",
abstract = "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-I-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 {\AA}. 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) {\AA}), which is noticeably larger than the sum of the covalent radii of the elements.",
keywords = "PHOSPHORUS, 2-COORDINATE, CHEMISTRY",
author = "Kornev, {Alexander N.} and Panova, {Yulia S.} and Sushev, {Vyacheslav V.} and {Dorado Daza}, {Diego F.} and Novikov, {Alexander S.} and Cherkasov, {Anton V.} and Fukin, {Georgy K.} and Abakumov, {Gleb A.}",
year = "2019",
month = dec,
day = "2",
doi = "10.1021/acs.inorgchem.9b02690",
language = "English",
volume = "58",
pages = "16144--16153",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "23",

}

RIS

TY - JOUR

T1 - The Nature of P(σ2λ3â"σ2λ1) Dualism

T2 - 3a,6a-Diaza-1,4-diphosphapentalene as a Form of Stabilized Singlet Phosphinidene

AU - Kornev, Alexander N.

AU - Panova, Yulia S.

AU - Sushev, Vyacheslav V.

AU - Dorado Daza, Diego F.

AU - Novikov, Alexander S.

AU - Cherkasov, Anton V.

AU - Fukin, Georgy K.

AU - Abakumov, Gleb A.

PY - 2019/12/2

Y1 - 2019/12/2

N2 - 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-I-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.

AB - 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-I-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.

KW - PHOSPHORUS

KW - 2-COORDINATE

KW - CHEMISTRY

UR - http://www.scopus.com/inward/record.url?scp=85075435561&partnerID=8YFLogxK

UR - https://pubs.acs.org/sharingguidelines https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b02690

UR - http://www.mendeley.com/research/nature-p%CF%83-2-%CE%BB-3-%CF%83-2-%CE%BB-1-dualism-3a6adiaza14diphosphapentalene-form-stabilized-singlet-phosphinidene

U2 - 10.1021/acs.inorgchem.9b02690

DO - 10.1021/acs.inorgchem.9b02690

M3 - Article

AN - SCOPUS:85075435561

VL - 58

SP - 16144

EP - 16153

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 23

ER -

ID: 49515389