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Synthesis and structure of para‐toluene sulfonamide lanthanide complexes and their application in the polymerization of ε‐caprolactone
Author(s) -
Wang LiJun,
Peng Ling,
Cen Bo,
Wang YuLong,
Tao Xian,
Shen YingZhong
Publication year - 2017
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.3828
Subject(s) - chemistry , denticity , homoleptic , lanthanide , toluene , polymerization , crystal structure , amine gas treating , medicinal chemistry , infrared spectroscopy , chelation , ring opening polymerization , proton nmr , polymer chemistry , crystallography , stereochemistry , inorganic chemistry , organic chemistry , metal , polymer , ion
A series of para‐toluene sulfonamide ligands [TsNHPr‐i( HL 1 ), TsNHBu‐t( HL 2 ), TsNHPh( HL 3 ), TsNHPhMe‐p( HL 4 ), TsNHPhOMe‐p( HL 5 )] were synthesized by amidation using para‐toluene sulfonyl chloride reacting with different primary amines. A series of homoleptic lanthanide complexes (Ln L 3 , 1–10) (Ln = La, L = L 1 ( 1 ), Ln = Gd, L = L 2 ( 2 ), Ln = La, L = L 2 ( 3 ), Ln = Gd, L = L 2 ( 4 ), Ln = La, L = L 3 ( 5 ), Ln = Gd, L = L 3 ( 6 ), Ln = La, L = L 4 ( 7 ), Ln = Gd, L = L 4 ( 8 ), Ln = La, L = L 5 ( 9 ), Ln = Gd, L = L 5 ( 10 )) were prepared by amine elimination reactions of the ligands with Ln[N(SiMe 3 ) 2 ] 3 (Ln = La, Gd). Complexes 1 , 3 , 5 , 7 and 9 were all characterized by NMR spectra, and the structures of complex 3 was determined by single‐crystal X‐ray diffraction. Complex 3 crystallizes a binuclear cluster, consisting of two La 3+ and six (TsNBu‐t) − anions. Three (TsNBu‐t) − anions are chelating to each La 3+ as bidentate model with O and N forming three‐membered chelate rings; one of three anions is bridging to another La 3+ via oxygen. All complexes were characterized using elemental analysis and infrared spectra. The catalytic properties of complexes 1–10 for the ring‐opening polymerization of ε‐caprolactone were studied and the results showed that all complexes are efficient initiators for this ring‐opening polymerization reaction.