Two different faces of the triangular cluster Rh3Cp3(μ2-CO)3 towards metalloelectrophiles: Structural and theoretical study

The tetrahedral clusters [(C4Me4)CoRh3Cpʹ3(μ3-CO)3]+ (2; Cpʹ = C5H4Me) and [(Ph3P)AuRh3Cpʹ3(μ2-CO)3]+ (3) were synthesized by reactions of Rh3Cpʹ3(μ2-CO)3 (1b) with metalloelectrophiles [(C4Me4)Co]+ (generated from [(C4Me4)Co(C6H6)]+ under visible-light irradiation) and [(Ph3P)Au]+ (generated from (Ph3P)AuCl/Tl+). They were isolated as salts with PF6− anion, and the structures of 2PF6 and 3PF6 were determined by X-ray diffraction. The structural data gave evidence that the coordination of [(C4Me4)Co]+ occurs to the face of 1b with the CO ligands, while the [(Ph3P)Au]+ species reacts with the opposite face of 1b. The latter interaction is accompanied by elongation of the Rh–Rh bonds within the rhodium triangle by 0.1 Å. DFT calculations (at the BP86/TZP level) revealed that the selectivity of the metalloelectrophile coordination is determined by orbital control. © 2020 Elsevier B.V.

Авторы
Loginov D.A.1, 2 , Nelyubina Y.V. 1 , Chusova O. 3
Язык
Английский
Статус
Опубликовано
Номер
121432
Том
924
Год
2020
Организации
  • 1 A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991, Russian Federation
  • 2 Plekhanov Russian University of Economics, Stremyannyi Pereulok 36, Moscow, 117997, Russian Federation
  • 3 Faculty of Science, RUDN University, 6 Miklukho-Maklaya St., Moscow, 117198, Russian Federation
Ключевые слова
Clusters; Density functional theory calculations; Metal–metal interactions; Rhodium
Дата создания
02.11.2020
Дата изменения
02.11.2020
Постоянная ссылка
https://repository.rudn.ru/ru/records/article/record/64363/