期刊
ORGANOMETALLICS
卷 28, 期 15, 页码 4464-4474出版社
AMER CHEMICAL SOC
DOI: 10.1021/om900300w
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资金
- MIUR [2005035123, 2007HMTJWP_002]
- European Network PAILLAIDIUM [HPRN-CT-2002-00196]
Two pairs of enantiomerically pure chiral bidentate nitrogen-donor ligands (N*-N) featuring one sp(3) and one sp(2) nitrogen atom have been applied to the CO/vinyl arene copolymerization reaction catalyzed by the corresponding monocationic palladium(11) complexes [Pd(CH3)(CH3CN)-(N*-N)][PF6]. The ligand frame containing the sp(2) nitrogen atom is a 2-pyridinyl or an 8-quinolinyl building block, while the chiral framework of the ligand derives from (S)-(+)-2.2'-(2-azapropane-1,3-diyl)-1,1'-binaphthalene or from trans-2.5-dimethylpyrrolidinyl. Ligands with the binaphthyl moiety generate catalysts showing a moderate activity, while ligands having the pyrrolidinyl fragment results in very low activity species. The stereochemistry of the synthesized polyketones depends of the sp(2) nitrogen-containing fragment: ligands with the 2-pyridinyl group lead to atactic copolymers, whereas those with the quinolinyl moiety give an isotactic polyketone. The effect of the nature of the quinone, added to the reaction mixture as oxidant, has been investigated MALDI-TOF analysis reveals the formation of several polymeric chains, differing in the presence of various end-groups.
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