Determination of the Absolute Configuration of CN-Palladacycles by 31P{1H} NMR Spectroscopy Using (1R,2S,5R)-Menthyloxydiphenylphosphine as the Chiral Derivatizing Agent: Efficient Chirality Transfer in Phosphinite Adducts

A series of (1R)-MenOPPh2 phosphinite derivatives of α-arylalkylaminate CN-palladacycles of known absolute configuration was prepared. Their structure and stereochemistry were determined using different experimental (NMR spectroscopy and X-ray diffraction) and theoretical (density functional theory calculation) methods. Despite the conformational mobility of the phosphinite reagent and the highly remote position of its stereocenters from those of the cyclopalladated amine, efficient chirality transfer in the phosphinite cyclopalladated complexes was established. On the basis of these results, a new method for the determination of the absolute configuration of chiral CN-palladacycles was elaborated using the (1R)-MenOPPh2 phosphinite as a highly sensitive referee ligand and in situ 31P{1H} NMR spectroscopy as a control method. The proposed approach is a remarkable addition to the classical NMR techniques, increasing their versatility and excluding the isolation of the phosphinite derivatives. © 2016 American Chemical Society.

Авторы
Gorunova O.N.1 , Novitskiy I.M.2 , Grishin Y.K.2 , Gloriozov I.P.2 , Roznyatovsky V.A.2 , Khrustalev V.N. 1, 3 , Kochetkov K.A.1 , Dunina V.V.2
Редакторы
-
Журнал
Издательство
American Chemical Society
Номер выпуска
2
Язык
Английский
Страницы
75-90
Статус
Опубликовано
Подразделение
-
Номер
-
Том
35
Год
2016
Организации
  • 1 A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Street 28, Moscow, 119991, Russian Federation
  • 2 Department of Chemistry, M.V. Lomonosov Moscow State University, Lenin Hills, Moscow, 119991, Russian Federation
  • 3 Inorganic Chemistry Department, Peoples' Friendship University of Russia, Miklukho-Maklay Street 6, Moscow, 117198, Russian Federation
Ключевые слова
Chirality; Nuclear magnetic resonance spectroscopy; Organometallics; X ray diffraction; Absolute configuration; Chirality transfer; Conformational mobility; Control methods; Cyclopalladated complexes; NMR techniques; Palladacycles; Stereocenters; Density functional theory
Дата создания
19.10.2018
Дата изменения
19.10.2018
Постоянная ссылка
https://repository.rudn.ru/ru/records/article/record/4018/