Document Detail


Synthesis of mono-amidinate-ligated rare-earth-metal bis(silylamide) complexes and their reactivity with [Ph(3)C][B(C(6)F(5))(4)], AlMe(3) and isoprene.
MedLine Citation:
PMID:  23340682     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
Amine elimination of rare-earth-metal tris(silylamide) complexes Ln[N(SiHMe(2))(2)](3)(THF)(x) (Ln = Sc, x = 1; Ln = Y, x = 2) with 1 equiv. of the amidines [PhC(N-2,6-R(2)C(6)H(3))(2)]H afforded a series of neutral mono(amidinate) rare-earth-metal bis(silylamide) complexes [PhC(N-2,6-R(2)C(6)H(3))(2)]Ln[N(SiHMe(2))(2)](2)(THF)(y) (R = Me, Ln = Sc, y = 0 (); R = Me, Ln = Y, y = 1 (); R = (i)Pr, Ln = Y, y = 1 ()). Treatment of with 1 equiv. of [Ph(3)C][B(C(6)F(5))(4)] in THF generated the corresponding cationic amidinate rare-earth-metal mono(silylamide) complexes [{PhC(N-2,6-R(2)C(6)H(3))(2)}Ln{N(SiHMe(2))(2)}(THF)(3)][B(C(6)F(5))(4)] (R = Me, Ln = Sc (), Y (); R = (i)Pr, Ln = Y ()). When were first activated with 1 equiv. of [Ph(3)C][B(C(6)F(5))(4)] in toluene, then treatment with THF gave the unexpected cationic amidinate rare-earth-metal amide complexes [{PhC(N-2,6-R(2)C(6)H(3))(2)}LnN{SiHMe(2)}{SiMe(2)N(SiHMe(2))(2)}(THF)(n)][B(C(6)F(5))(4)] (R = Me, Ln = Sc, n = 2 (); R = Me, Ln = Y, n = 4 (); R = (i)Pr, Ln = Y, n = 2 ()). The reaction of with excess AlMe(3) produced the heterometallic Ln/Al methyl complexes [PhC(N-2,6-R(2)C(6)H(3))(2)]Ln[(μ-Me)(2)AlMe(2)](2) (R = Me, Ln = Sc (), Y (); R = (i)Pr, Ln = Y ()). All these complexes were well-characterized by elemental analysis, NMR spectroscopy and FT-IR spectroscopy. , and were further structurally authenticated by X-ray crystallography. The binary catalyst system of /[Ph(3)C][B(C(6)F(5))(4)] in toluene showed activity toward 3,4-selective polymerization of isoprene, whilst the tertiary catalyst systems of /[Ph(3)C][B(C(6)F(5))(4)]/AlMe(3) were highly active for cis-1,4-selective polymerization of isoprene.
Authors:
Yunjie Luo; Yinlin Lei; Shimin Fan; Yibin Wang; Jue Chen
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-23
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-23     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Organometallic Chemistry Laboratory, Ningbo Institute of Technology, Zhejiang University, Ningbo 315100, People's Republic of China. lyj@nit.zju.edu.cn.
Export Citation:
APA/MLA Format     Download EndNote     Download BibTex
MeSH Terms
Descriptor/Qualifier:

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


Previous Document:  Inflammatory Bowel Disease in Chinese Children: A Multicenter Analysis Over a Decade from Shanghai.
Next Document:  [Indications and technique of fetal magnetic resonance imaging].