PMID- 29182167
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20180216
LR  - 20180216
IS  - 1477-9234 (Electronic)
IS  - 1477-9226 (Linking)
VI  - 46
IP  - 48
DP  - 2017 Dec 12
TI  - Effects of nucleophilic ligands on the chain initiation efficiency of polar 
      monomer polymerizations catalyzed by 2-methoxyethylaminobis(phenolate)yttrium 
      complexes: a DFT study.
PG  - 16993-16999
LID - 10.1039/c7dt04011c [doi]
AB  - 2-Methoxyethylaminobis(phenolate)yttrium complexes Y(ONOO(tBu))(Nu)(THF) have 
      unique catalytic activity and selectivity toward the ring-opening polymerization 
      (ROP) of beta-butyrolactone (BBL). Some of them also showed activity toward the 
      group-transfer polymerization (GTP) of Michael-type monomers. These complexes 
      with various nucleophilic ligands (Nu = CH(2)SiMe(3), 1a; N(SiHMe(2))(2), 1b; 
      OiPr, 1c) showed discrepant activity for ROP and GTP. The chain initiation of the 
      ROP of BBL and the GTP of 2-vinylpyridine (2VP) catalyzed by these complexes is 
      investigated by DFT calculations. The results indicate that, in the case of the 
      ROP of BBL, less steric hindrance of the nucleophilic anionic ligand OiPr makes 
      complex 1c have a higher chain initiation efficiency and thus a higher 
      polymerization activity than 1a and 1b. In the case of the GTP of 2VP, the 
      activity of 1a benefits from a good orbital match between the moieties of 
      Y-CH(2)SiMe(3) and vinyl of 2VP. The origin of the experimentally observed 
      inertness of 1b has also been elucidated. These results could add to the better 
      understanding of the experimentally observed activity discrepancy and shed light 
      on the development of such a catalysis system.
FAU - Yang, Jimin
AU  - Yang J
AD  - State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian 
      University of Technology, Dalian 116024, China. luoyi@dlut.edu.cn.
FAU - Yu, Yang
AU  - Yu Y
AD  - State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian 
      University of Technology, Dalian 116024, China. luoyi@dlut.edu.cn.
FAU - Qu, Jingping
AU  - Qu J
AUID- ORCID: 0000-0002-7576-0798
AD  - State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian 
      University of Technology, Dalian 116024, China. luoyi@dlut.edu.cn.
FAU - Luo, Yi
AU  - Luo Y
AUID- ORCID: 0000-0001-6390-8639
AD  - State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian 
      University of Technology, Dalian 116024, China. luoyi@dlut.edu.cn.
LA  - eng
PT  - Journal Article
PL  - England
TA  - Dalton Trans
JT  - Dalton transactions (Cambridge, England : 2003)
JID - 101176026
EDAT- 2017/11/29 06:00
MHDA- 2017/11/29 06:01
CRDT- 2017/11/29 06:00
PHST- 2017/11/29 06:00 [pubmed]
PHST- 2017/11/29 06:01 [medline]
PHST- 2017/11/29 06:00 [entrez]
AID - 10.1039/c7dt04011c [doi]
PST - ppublish
SO  - Dalton Trans. 2017 Dec 12;46(48):16993-16999. doi: 10.1039/c7dt04011c.