Document Detail


Co(III) imidos exhibiting spin crossover and C-H bond activation.
MedLine Citation:
PMID:  23043624     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
Using the dipyrrin ligand (ArLH = 5-mesityl-1,9-(2,4,6-triphenylphenyl)dipyrrin), four-coordinate CoII (ArL)CoCl(py) and a three-coordinate CoI complexes (ArL)Co(py) were synthesized and characterized. Reaction of (ArL)Co(py) with tBuN3 afforded an isolable three-coordinate, Co-imido complex (ArL)Co(NtBu) that is paramagnetic at room temperature. Variable-temperature 1H NMR and SQUID magnetometry revealed (ArL)Co(NtBu) undergoes a thermally induced spin-crossover from an S = 0 ground state to a quintet (S = 2) config-uration. Variable-temperature X-ray crystallography showed an elongation of the Co imido N bond, consistent with population of a molecular orbital featuring significant (Co-N) pi* character. Reaction of (ArL)Co(py) with mesityl azide yields an isolable S = 1, terminal imido complex, that converted via benzylic C-H activation into the metallacycloindoline (ArL)Co(2-NHC6H2-2,4-Me2-6-CH2).
Authors:
Evan R King; Theodore A Betley; Graham T Sazama
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-10-8
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  -     ISSN:  1520-5126     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-9     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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