Proof of Chiral Dihydride Complexes Including Catalyst and Substrate during the Bis(phosphinite)rhodium( I )‐Catalyzed Hydrogenation of Dimethyl Itaconate | Zendy

Harthun Andreas | Zendy; Kadyrov Renat | Zendy; Selke Rüdiger | Zendy; Bargon Joachim | Zendy

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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.

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