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Proof of Chiral Dihydride Complexes Including Catalyst and Substrate during the Bis(phosphinite)rhodium( I )‐Catalyzed Hydrogenation of Dimethyl Itaconate
Author(s) -
Harthun Andreas,
Kadyrov Renat,
Selke Rüdiger,
Bargon Joachim
Publication year - 1997
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199711031
Subject(s) - phosphinite , rhodium , catalysis , spin isomers of hydrogen , chemistry , substrate (aquarium) , octahedron , medicinal chemistry , stereochemistry , crystal structure , crystallography , organic chemistry , hydrogen , oceanography , geology
The PHIP‐NMR method (PHIP = parahydrogen induced polarization) can be used to detect dihydride catalyst–substrate complexes of the general formula [Rh(PP)(XX)(H) 2 ]BF 4 (shown on the right, XX = dimethyl itaconate as substrate), which are formed in situ under hydrogenation conditions with chiral bis(phosphinite)rhodium( I ) catalysts. Remarkable is the absence of typical (H,P) trans coupling ( 2 J (H,P) trans ); the RhP bond trans to H B is therefore lenthened, and the octahedral geometry distorted.