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An EPR Study of the Vanadium Species Formed upon Interaction of Vanadyl N and C-Capped tris(phenolate) Complexes with AlEt3 and AlEt2Cl Full article

Общее Language: Английский, Genre: Full article,
Status: Published, Source type: Original
Journal Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169
Output data Year: 2009, Volume: 303, Number: 1-2, Pages: 23-29 Pages count : 7 DOI: 10.1016/j.molcata.2008.12.013
Tags Copolymer, Cyclic carbonate, Ionic liquid
Authors Soshnikov Igor E. 1,2 , Semikolenova Nina V. 1 , Bryliakov Konstantin P. 1,2 , Zakharov Vladimir A. 1 , Redshaw Carl 3 , Talzi Evgenii P. 1,2
Affiliations
1 Boreskov Institute of Catalysis SB RAS
2 Novosibirsk State University
3 University of East Anglia

Funding (2)

1 Russian Foundation for Basic Research 06-03-32700
2 Royal Society 2006/R4-IJP

Abstract: Reactions of vanadyl N and C-capped tris(phenolate) complexes 1 and 2 (Scheme 1) with AlEt3 and AlEt2Cl, in the absence and in the presence of ethyltrichloroacetate (ETA), were monitored by EPR. It was shown, that vanadium(IV) complexes with proposed structures LNVIV(Et)(AlEt3) and LNVIV(Et)(AlEt2Cl) are formed at the initial stage of interaction of 1 with AlEt3 and AlEt2Cl, respectively (LN are unidentified products of interaction of the initial N-capped ligand and Vdouble bond; length as m-dashO moiety with aluminum alkyls). In the absence of re-activator (ETA), LNVIV(Et)(AlEt3) and LNVIV(Et)(AlEt2Cl) rapidly convert at room temperature to V(III) species, which relatively slowly transform to complexes LNVIIEt2 and LNVII(Et)Cl. Concentration of LNVIV(Et)(AlEt2Cl) dramatically increases in the presence of ETA, that correlates with the increase of the polymerization activity of the catalyst system 1/AlEt2Cl. The complex LNVIV(Et)(AlEt2Cl) can be precursor of the active species of polymerization. Similarly, ETA increases concentration of vanadium(IV) complex LCVIV(Et)(AlEt2Cl) in the catalyst system 2/AlEt2Cl (LC are unidentified products of interaction of the initial C-capped ligand and Vdouble bond; length as m-dashO moiety with aluminum alkyls). The complex LCVIV(Et)(AlEt2Cl) can be precursor of the active species of polymerization.
Cite: Soshnikov I.E. , Semikolenova N.V. , Bryliakov K.P. , Zakharov V.A. , Redshaw C. , Talzi E.P.
An EPR Study of the Vanadium Species Formed upon Interaction of Vanadyl N and C-Capped tris(phenolate) Complexes with AlEt3 and AlEt2Cl
Journal of Molecular Catalysis A: Chemical. 2009. V.303. N1-2. P.23-29. DOI: 10.1016/j.molcata.2008.12.013 publication_identifier_short.wos_identifier_type publication_identifier_short.scopus_identifier_type publication_identifier_short.rinz_identifier_type
Dates:
Submitted: Nov 1, 2008
Accepted: Dec 18, 2008
Published online: Dec 30, 2008
Published print: Apr 15, 2009
Identifiers:
publication_identifier.wos_identifier_type WOS:000265804600004
publication_identifier.scopus_identifier_type 2-s2.0-77953308725
publication_identifier.rinz_identifier_type 20546114
publication_identifier.accession_number_identifier_type 2009:442221
publication_identifier.chemical_accession_number_identifier_type 151:508895
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