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A heteroleptic cyclometalated iridium(iii) fluorophenylpyridine complex from partial defluorohydrogenation reaction: synthesis, photophysical properties and mechanistic insights.
MedLine Citation:
PMID:  23348919     Owner:  NLM     Status:  Publisher    
In this paper, a C-F bond activation reaction of a chloro-bridged iridium(iii) dimer (dfppy)(2)Ir(μ-Cl)(2)Ir(dfppy)(2) () (dfppy denotes 2-(4,6-difluorophenyl)pyridyl) in the presence of sodium methoxide has been reported, leading to the formation of a heteroleptic cyclometalated iridium(iii) fluorophenylpyridine complex . HPLC-mass analysis confirmed the release of formaldehyde in the product mixture. When sodium benzyloxide was used as the base, complex was also generated with the release of a benzaldehyde derivative. Complex has been fully characterized by (1)H-NMR, (19)F-NMR and X-ray crystallographic methods, confirming the partial loss of one of the fluorine atoms on one of the cyclometalated phenylpyridyl ligands. Photophysical studies of complex show that it has a similar absorption spectrum to that of Ir(iii)(dfppy)(3). However, the emission spectrum shows a red shift maximum emission band at 478 nm due to the loss of a single fluorine atom, highlighting the critical effect of fluorine on the photoluminescence of these Ir(iii) complexes. Finally, intensive mechanistic studies including HPLC-mass analysis, (1)H-NMR, and (19)F-NMR studies demonstrate that the formation of complex should involve a critical β-hydride elimination of Ir(iii)-alkoxide intermediate and the participation of Ir-hydride and/or Ir-fluoride intermediates.
Liang Li; Feng Wu; Songlin Zhang; Dawei Wang; Yuqiang Ding; Zhenzhong Zhu
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-25
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-25     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu Province, China.
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