Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine Научная публикация
Журнал |
Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
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Вых. Данные | Год: 2024, Том: 63, Номер: 1, Страницы: 369–380 Страниц : DOI: 10.1021/acs.inorgchem.3c03271 | ||||
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Организации |
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Реферат:
There is unceasing interest toward transformations of phosphine derivatives, which are facilitated by transition metals. We report a facile Pd(II)- and Pt(II)-assisted P–C bond cleavage in a luminescent 2-phenylbenzothiazole-based α-methylaminophosphine (PCN, 1). Specifically, reactions between 1 and [M(COD)Cl2] (M = Pd, Pt; COD = cycloocta-1,5-diene) in different solvents (methylene chloride, acetonitrile, pyridine, toluene) resulted in the formation of PPh2–, captured either as a bridging ligand in binuclear complexes with a {M2(PPh2)2} moiety or as an adduct to COD in [Pt2(PPh2COD)2Cl2]. The heterocyclic part transforms to annulated c-CN+ species with a 1,2-dihydroquinazoline cycle formed. In the presence of pyridine as a base, annulated form c-CN+ destabilizes and undergoes reverse cyclization transforming to deprotonated CN form. Quantum-chemical density functional theory (DFT) calculations predict that a crucial step in the reactions involves proton transfer from the N atom of the amino group of PCN to a neighboring molecule. A combination of high photophysical sensitivity of c-CN+ toward its immediate environment and rich structural capabilities in assembling (c-CN)22+ pairs in different crystal packings in a family of phases with the general formula (c-CN)2[M2(PPh2)2Cl4] allows one to fine-tune the luminescence properties of the latter. The results were rationalized as a variation of π–π intercationic spacings, which tunes the degree of excited-state charge transfer between c-CN+ cations. As a result, compounds with relatively short interplanar π–π-separation between the cations show a stronger charge-transfer-mediated bathochromic shift.
Библиографическая ссылка:
Afonin M.Y.
, Martynenko P.A.
, Kolybalov D.S.
, Khisamov R.M.
, Konchenko S.N.
, Sukhikh T.S.
Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine
Inorganic Chemistry. 2024. V.63. N1. P.369–380. DOI: 10.1021/acs.inorgchem.3c03271 WOS Scopus РИНЦ OpenAlex
Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine
Inorganic Chemistry. 2024. V.63. N1. P.369–380. DOI: 10.1021/acs.inorgchem.3c03271 WOS Scopus РИНЦ OpenAlex
Даты:
Поступила в редакцию: | 18 сент. 2023 г. |
Принята к публикации: | 10 нояб. 2023 г. |
Опубликована online: | 21 нояб. 2023 г. |
Опубликована в печати: | 8 янв. 2024 г. |
Идентификаторы БД:
Web of science: | WOS:001138319200001 |
Scopus: | 2-s2.0-85178569455 |
РИНЦ: | 64089671 |
OpenAlex: | W4388851851 |