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Syntheses, Cycloaminocarbonylation and Amidination of Rare Earth o-Aminobenzamido Dianion Complexes Bearing Cyclopentadienyl Co-ligand
Author NameAffiliationE-mail
SUN Yan Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China  
LIU Rui-Ting Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China  
WENG Lin-Hong Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China  
ZHOU Xi-Geng Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China
State Key Laboratory of Organometallic Chemistry, Shanghai 200032, China 		xgzhou@fudan.edu.cn 
Abstract: Treatment of Cp3Ln with o-aminobenzamide followed by crystallization in a HMPA and toluene mixture affords the tetranuclear organolanthanide complexes [CpLn( μ-η2:η2-NHC6H4CONH)( μ3-η1:η1:η2-NHC6H4CONH)LnCp(HMPA)}2 (Ln=Yb, 1a; Er, 1b; Y, 1c). Reaction of 1 with PhNCO (nPhNCO/n1=4) in toluene gives the dianionic quinazolyldiolate (Quo) complexes [Cp2Ln( μ3-η2:η2:η1-Quo)]3Ln(HMPA)2 (Ln=Yb, 2a; Er, 2b; Y, 2c), indicating that one isocyanate molecule can undergo the tandem reaction with both NH and CONH of 1 to construct a quinazoly-ldiolate skeleton, companying with the elimination of PhNH2. However, 1a~1c react with iPrN=C=NiPr under the same conditions to give only the single ArNH addition products {Cp2Ln[ μ-η1:η1:η2-iPrNC(NHiPr)NC6H4 CONH]}3Ln(HMPA)3 (Ln=Yb, 3a; Er, 3b; Y, 3c). Furthermore, treatment of Cp3Ln with o-aminobenzamide followed by reacting with iPrN=C=NiPr gave {CpLn[ μ-η1:η2:η2-NHCOC6H4NC(NHiPr)NiPr]}2 (Ln=Yb, 4a; Er, 4b; Y, 4c). Noticeably, HMPA could induce the transformation of 4 into 3 by a ligand redistribution.
Keywords: lanthanide complexes  cycloaminocarbonylation  isocyanate  o-aminobenzamide  addition
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SUN Yan,LIU Rui-Ting,WENG Lin-Hong,ZHOU Xi-Geng.Syntheses, Cycloaminocarbonylation and Amidination of Rare Earth o-Aminobenzamido Dianion Complexes Bearing Cyclopentadienyl Co-ligand[J].Chinese Journal of Inorganic Chemistry,2017,33(11):2124-2138.
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Chinese Journal of Inorganic Chemistry