Novel Catalyst Systems Based on Cationic Palladium Cyclopentadienyl Complexes for the Polymerization of Norbornene and Norbornene Derivatives

Novel Catalyst Systems Based on Cationic Palladium Cyclopentadienyl Complexes for the Polymerization of Norbornene and Norbornene Derivatives Научная публикация

Журнал

Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210

Вых. Данные

Год: 2024, Том: 65, Номер: 1, Страницы: 40-56 Страниц : 17 DOI: 10.1134/s0023158424010087

Авторы

Suslov D.S. ^1,2 , Pakhomova M.V. ^1,2 , Bykov M.V. ^1,2 , Orlov T.S. ^2,3 , Abramov Z.D. ^1,2 , Suchkova A.V. ² , Abramov P.A. ⁴

Организации

1	Faculty of Chemistry, Irkutsk State University, Irkutsk, 664003 Russia
2	Research Institute of Oil and Coal Chemical Synthesis, Irkutsk State University, Irkutsk, 664003 Russiaa
3	School of High Technologies, Irkutsk National Research Technical University, Irkutsk, 664074 Russia
4	Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia

Results of studying the catalytic properties of systems based on complexes with [Pd(Cp)(L)n]m[BF4]m (where Cp = η5-C5H5; n = 2, m = 1: L = tris(ortho-methoxyphenyl)phosphine, triphenylphosphine, tris(2-furyl)phosphine (TFP); n = 1, m = 1: L = 1,1'-bis(diphenylphosphino)ferrocene, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane; n = 1, m = 2 or 3: L = 1,6-bis(diphenylphosphino)hexane) in the addition homo- and copolymerization of norbornene (NB) and NB derivatives have been described. It has been found that these complexes can be activated with Lewis acids (BF3⋅OEt2 or AlCl3). The productivity of the [Pd(Cp)(PPh3)2][BF4]/BF3⋅OEt2 catalyst system in NB polymerization can achieve 188 800 molNB. The homopolymerization of 5-methoxycarbonylnorbornene and the copolymerization of NB with 5-methoxycarbonylnorbornene or 5-phenylnorbornene in the presence of BF3⋅OEt2 and [Pd(Cp)(L)2][BF4] (L = PPh3 or TFP) has been studied. A hypothesis for the formation of the catalyst via the intramolecular rearrangement of the η5-Cp ligand into the η1-Cp form upon interaction with a Lewis acid has been proposed. The structure of the [Pd(Cp)(TFP)2]BF4 complex (I) has been determined by X-ray diffraction (XRD) analysis. In the crystal structure of complex I, the coordination sphere of palladium is characterized by a slight distortion of the square planar geometry of the central atom, while the cyclopentadiyl moiety is in an eclipsed conformation. Based on XRD data, the steric hindrance of the TFP ligand has been determined (cone angle is 149°).

Suslov D.S. , Pakhomova M.V. , Bykov M.V. , Orlov T.S. , Abramov Z.D. , Suchkova A.V. , Abramov P.A.
Novel Catalyst Systems Based on Cationic Palladium Cyclopentadienyl Complexes for the Polymerization of Norbornene and Norbornene Derivatives
Kinetics and Catalysis. 2024. V.65. N1. P.40-56. DOI: 10.1134/s0023158424010087 WOS Scopus РИНЦ CAPlus OpenAlex

Суслов Д.С. , Пахомова М.В. , Быков М.В. , Орлов Т.С. , Абрамов З.Д. , Сучкова А.В. , Абрамов П.А.
Новые каталитические системы для полимеризации норборнена и его производных на основе катионных циклопентадиенильных комплексов палладия
Кинетика и катализ. 2024. Т.65. №1. С.48-66. DOI: 10.31857/S0453881124010058 РИНЦ OpenAlex

Поступила в редакцию:	9 авг. 2023 г.
Принята к публикации:	5 окт. 2023 г.
Опубликована online:	27 апр. 2024 г.

Web of science:	WOS:001210717700002
Scopus:	2-s2.0-85191653495
РИНЦ:	66913098
Chemical Abstracts:	2024:924976
OpenAlex:	W4395698218

БД	Цитирований
OpenAlex	1
Scopus	1