Reaction of a Rhodium-MiniPHOS complex with dihydrogen: NMR and computational study

Ilya D. Gridnev, Tsuneo Imamoto

Research output: Contribution to journalArticlepeer-review

33 Citations (Scopus)


The rhodium-MiniPHOS complex [Rh((R,R)-MeButPCH2 PMeBut)2]+BF4- (1) is reversibly and stereoselectively hydrogenated at low temperatures to give one isomer of cis-dihydride 2a. The second possible diastereomer, 2b, is not observed experimentally. DFT calculations suggest that 2b is 3.5 kcal mol-1 less stable than 2a. The parameters of the equilibrium between 2a, 1, and H2 determined by NMR are ΔH = -7.7 ± 0.1 kcal mol-1 and ΔS = -25 ± 1 cal mol-1 K-1. Formation of the trans-dihydride 3 is observed at around -20°C. Most probably 3 is formed by isomerization of 2a or 2b. This isomerization involves reversible dissociation of the Rh-P bond. Similar dissociation of the Rh-P bond in 2a might make possible the substrate binding when 1 is used as a catalyst for asymmetric hydrogenation.

Original languageEnglish
Pages (from-to)545-549
Number of pages5
Issue number3
Publication statusPublished - 2001 Feb 5
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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