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Nickel complexes incorporating an amido phosphine chelate with a pendant amine arm: Synthesis, structure, and catalytic Kumada coupling.
MedLine Citation:
PMID:  22124467     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
A series of organonickel(ii) complexes incorporating an amido phosphine ligand tethered with an amino pendant have been prepared and characterized. Deprotonation of N-(dimethylaminoethyl)-2-diphenylphosphinoaniline (H[PNN]) with one equivalent of n-BuLi in ethereal or hydrocarbon solutions at -35 °C generates cleanly dimeric {Li[PNN]}(2) as yellow crystals. The reaction of NiCl(2)(DME) with {Li[PNN]}(2) in THF at -35 °C affords green crystalline [PNN]NiCl. Treating [PNN]NiCl with NaX in acetone solutions gives [PNN]NiX (X = Br, I). Alkylation or arylation of [PNN]NiCl with appropriate Grignard reagents in THF at -35 °C produces red crystalline [PNN]NiR (R = Me, Et, i-Bu, n-hexyl, CH(2)Ph, Ph). The chloride complex [PNN]NiCl was found to be an active catalyst precursor for Kumada coupling reactions of PhX (X = I, Br, Cl) with aryl or alkyl Grignard reagents, including those containing β-hydrogen atoms. The X-ray structures of {Li[PNN]}(2) and [PNN]NiX (X = Cl, Br, Me, Et, n-hexyl) are reported.
Authors:
Lan-Chang Liang; Wei-Ying Lee; Yu-Ting Hung; Yi-Chen Hsiao; Liang-Chien Cheng; Wei-Chen Chen
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2011-11-29
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  -     Publication Date:  2011 Nov 
Date Detail:
Created Date:  2011-11-29     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Department of Chemistry and Center for Nanoscience & Nanotechnology, National Sun Yat-sen University, Kaohsiung, 80424, Taiwan. lcliang@mail.nsysu.edu.tw.
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