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Synthesis of Octahedral Hydrido(vinyl)iridium( III ) Complexes by CH Activation: An Example of a Thermodynamically Favored Rearrangement [M(CHRCHX)]→[M(H)(CRCHX)]
Author(s) -
Werner Helmut,
Dirnberger Thomas,
Schulz Michael
Publication year - 1988
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.198809481
Subject(s) - olefin fiber , chemistry , yield (engineering) , iridium , methyl acrylate , medicinal chemistry , metal , octahedron , stereochemistry , photochemistry , crystallography , crystal structure , catalysis , organic chemistry , materials science , polymer , copolymer , metallurgy
The detection of an olefin‐metal complex as the primary product of the reaction of an olefin with a coordinatively unsaturated complex fragment is just as surprising as the finding that the product of a CH addition is more stable than the corresponding olefin complex. Starting from the five‐coordinate hydridoiridium( III ) compounds 1 , the hydrido(vinyl)‐complexes 2 are formed in almost quantitative yield on reaction with olefins of the type H 2 CCR 1 COR 2 (R 1 H, Me; R 2 Me, OMe) at 80°C. Another route to 2 , R 1 H, R 2 OMe, starts from 4. This reacts with methyl acrylate at room temperature to give the squre‐planar olefin complex 3 , which isomerizes on irradiation. No back reaction takes place, either thermally or photochemically.