Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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 изданиях › статья › Рецензирование
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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