Cyclobutadiene Arene Complexes of Rhodium and Iridium

Reactions of [(C2H4)2RhCl]2 or [(coe)2RhCl]2 (coe = cyclooctene) with AgPF6 and arenes, followed by addition of 3-hexyne, give the cyclobutadiene complexes [(C4Et4)Rh(arene)]+ in 40-65% yield (arene = tert-butylbenzene, p-xylene, mesitylene, 4-mesitylbutanoic acid). In the absence of arenes, the hexaethylbenzene complex [(C4Et4)Rh(C6Et6)]+ is formed in 70% yield as a result of cyclotrimerization of 3-hexyne in the coordination sphere of rhodium. Similar reaction of [(coe)2IrCl]2 with AgPF6 and 3-hexyne leads to [(C4Et4)Ir(C6Et6)]+, which is apparently the first reported cyclobutadiene iridium complex. DFT calculations suggest that formation of the model cyclobutadiene complex [(C4Me4)Rh(C6H6)]+ from bis(alkyne) intermediate [(C2Me2)2Rh(C6H6)]+ can proceed via a metallacycle transition state with a low energy barrier of 14.5 kcal mol-1. © 2016 American Chemical Society.

Авторы
Shvydkiy N.V.1 , Trifonova E.A.1 , Shved A.M.1 , Nelyubina Y.V.1 , Chusov D. 1 , Perekalin D.S. 1, 2 , Kudinov A.R.1
Журнал
Издательство
American Chemical Society
Номер выпуска
17
Язык
Английский
Страницы
3025-3031
Статус
Опубликовано
Том
35
Год
2016
Организации
  • 1 Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova Street, Moscow, 119991, Russian Federation
  • 2 Department of Organic Chemistry, RUDN University, 6 Miklukho-Maklaya Street, Moscow, 117198, Russian Federation
Ключевые слова
Aromatic compounds; Butadiene; Coordination reactions; Iridium; Iridium compounds; Rhodium; Arene complexes; Coordination sphere; Cyclobutadiene complexes; Cyclobutadienes; Cyclotrimerization; DFT calculation; Tert-butylbenzene; Transition state; Rhodium compounds
Дата создания
19.10.2018
Дата изменения
19.10.2018
Постоянная ссылка
https://repository.rudn.ru/ru/records/article/record/3813/