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Synthesis and Structural Characterization of β‐Diketiminato Yttrium Complexes and their Application in Epoxide/CO 2 ‐Copolymerization
Author(s) -
Lazarov Boyan B.,
Hampel Frank,
Hultzsch Kai C.
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700246
Subject(s) - cyclohexene oxide , copolymer , chemistry , epoxide , yttrium , octahedron , ligand (biochemistry) , amine gas treating , catalysis , dispersity , medicinal chemistry , cyclohexene , stereochemistry , polymer chemistry , oxide , crystallography , crystal structure , organic chemistry , biochemistry , receptor , polymer
The β‐diketiminato yttrium complexes [(BDI Ph ) 2 Y{N(SiHMe 2 ) 2 }] ( 1 , BDI Ph = [PhNC(Me)CHC(Me)NPh] − ), [(BDI Ph ) 3 Y] ( 2 ), and [(C 5 Me 5 )(BDI Ph )Y{N(SiHMe 2 ) 2 }] ( 4 ) are available via amine elimination starting from (BDI Ph )H and either [Y{N(SiHMe 2 ) 2 } 3 (THF) 2 ] or [(C 5 Me 5 )Y{N(SiHMe 2 ) 2 } 2 (THF)] ( 3 ). X‐ray crystallographic analysis of complexes 1 and 4 revealed a η 5 coordination mode for the β‐diketiminato ligand, whereas the distorted octahedral complex 2 displayed pure κ 2 coordination. Complex 3 was also structurally characterized. 1 , 3 , and 4 are moderately active catalysts in the copolymerization of cyclohexene oxide and CO 2 . Complex 3 was the most active system (TOF up to 33 h −1 at 75 °C, 8.5 atm CO 2 ) and gave the highest molecular weight and narrowest polydispersity ( M n = 12600 g mol −1 , M w / M n = 1.6).