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Organochromium Complexes Bearing Noninnocent Diimine Ligands
Author(s) -
Kreisel Kevin A.,
Yap Glenn P. A.,
Theopold Klaus H.
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100803
Subject(s) - diimine , chemistry , ligand (biochemistry) , medicinal chemistry , cationic polymerization , isopropyl , substituent , stereochemistry , reductive elimination , aryl , photochemistry , alkyl , organic chemistry , biochemistry , receptor , catalysis
We have prepared several anionic and neutral organochromium complexes featuring noninnocent α‐diimine ligands. All neutral and anionic complexes refrain from insertion of the C=N bonds of the diimine ligand into the chromium–carbon bonds, presumably due to the reduced nature of the diimine ligand. However, insertion can be facilitated by one‐electron oxidation. Thus, oxidation of [( H L i Pr )CrR(THF)] [ H L i Pr = Ar–N=C(H)–(H)C=N–Ar in which Ar = 2,6‐diisopropylphenyl and R = CH 2 SiMe 3 or CH 3 ] with [(C 5 H 5 ) 2 Fe] + presumably forms [( H L i Pr )CrR(THF)] + , which contains a neutral diimine ligand coordinated to Cr II . This cationic complex apparently undergoes immediate insertion of the C=N bond of the diimine ligand into the Cr–alkyl bond, followed by C–H activation of the isopropyl substituent of an N–aryl group on the diimine ligand. DFT calculations confirm that [( H L i Pr )CrR(THF)] + contains a neutral innocent diimine ligand that undergoes C=N bond insertion into the Cr–R bond.