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Article: Carbon-Bridged Bis(phenolato)lanthanide Alkoxides: Syntheses, Structures, and Their Application in the Controlled Polymerization of ε-Caprolactone

TitleCarbon-Bridged Bis(phenolato)lanthanide Alkoxides: Syntheses, Structures, and Their Application in the Controlled Polymerization of ε-Caprolactone
Authors
Issue Date2005
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2005, v. 44 n. 14, p. 5133-5140 How to Cite?
AbstractA convenient method for the synthesis of lanthanide alkoxo complexes supported by a carbon-bridged bis(phenolate) ligand 2,2'-methylenebis(6-tert-butyl-4-methylphenoxo) (MBMP2-) is described. The reaction of (C5H5)3Nd with MBMPH2 in a 1:1 molar ratio in THF gave the bis(phenolato)lanthanide complex (C5H5)Nd(MBMP)(THF)2 (1) in a nearly quantitative yield. Complex 1 further reacted with 1 equiv of 2-propanol in THF to yield the bis(phenolato)lanthanide isopropoxide [(MBMP)2Nd(mu-OPr(i))(THF)2]2 (2) in high yield. Complex 2 can also be synthesized by the direct reaction of (C5H5)3Nd with MBMPH2 in a 1:1 molar ratio and then with 1 equiv of 2-propanol in situ in THF. Thus, the analogue bis(phenolato)lanthanide alkoxides [(MBMP)2Ln(mu-OR)(THF)2]2 [R = Pr(i), Ln = Yb (3); R = Me, Ln = Nd (4), Yb (5); R = CH2Ph, Ln = Nd (6), Yb (7)] were obtained by the reactions of (C5H5)3Ln (Ln = Nd, Yb) with MBMPH2 and then with 2-propanol, methanol, or benzyl alcohol, respectively. The ytterbium complex {[(MBMP)2Yb(THF)2]2(mu-OCH2Ph)(mu-OH)} (8) was also isolated as a byproduct. The single-crystal structural analyses of complexes 1-3 and 8 revealed that the coordination geometry around lanthanide metal can be best described as a distorted tetrahedron in complex 1 and as a distorted octahedron in complexes 2, 3, and 8. A O-H...Yb agostic interaction was observed in complex 8. Complexes 2-7 were shown to be efficient catalysts for the controlled polymerization of epsilon-caprolactone.
Persistent Identifierhttp://hdl.handle.net/10722/70363
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorYao, YMen_HK
dc.contributor.authorXu, Xen_HK
dc.contributor.authorLiu, Ben_HK
dc.contributor.authorZhang, Yen_HK
dc.contributor.authorShen, Qen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:22:09Z-
dc.date.available2010-09-06T06:22:09Z-
dc.date.issued2005en_HK
dc.identifier.citationInorganic Chemistry, 2005, v. 44 n. 14, p. 5133-5140en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70363-
dc.description.abstractA convenient method for the synthesis of lanthanide alkoxo complexes supported by a carbon-bridged bis(phenolate) ligand 2,2'-methylenebis(6-tert-butyl-4-methylphenoxo) (MBMP2-) is described. The reaction of (C5H5)3Nd with MBMPH2 in a 1:1 molar ratio in THF gave the bis(phenolato)lanthanide complex (C5H5)Nd(MBMP)(THF)2 (1) in a nearly quantitative yield. Complex 1 further reacted with 1 equiv of 2-propanol in THF to yield the bis(phenolato)lanthanide isopropoxide [(MBMP)2Nd(mu-OPr(i))(THF)2]2 (2) in high yield. Complex 2 can also be synthesized by the direct reaction of (C5H5)3Nd with MBMPH2 in a 1:1 molar ratio and then with 1 equiv of 2-propanol in situ in THF. Thus, the analogue bis(phenolato)lanthanide alkoxides [(MBMP)2Ln(mu-OR)(THF)2]2 [R = Pr(i), Ln = Yb (3); R = Me, Ln = Nd (4), Yb (5); R = CH2Ph, Ln = Nd (6), Yb (7)] were obtained by the reactions of (C5H5)3Ln (Ln = Nd, Yb) with MBMPH2 and then with 2-propanol, methanol, or benzyl alcohol, respectively. The ytterbium complex {[(MBMP)2Yb(THF)2]2(mu-OCH2Ph)(mu-OH)} (8) was also isolated as a byproduct. The single-crystal structural analyses of complexes 1-3 and 8 revealed that the coordination geometry around lanthanide metal can be best described as a distorted tetrahedron in complex 1 and as a distorted octahedron in complexes 2, 3, and 8. A O-H...Yb agostic interaction was observed in complex 8. Complexes 2-7 were shown to be efficient catalysts for the controlled polymerization of epsilon-caprolactone.-
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleCarbon-Bridged Bis(phenolato)lanthanide Alkoxides: Syntheses, Structures, and Their Application in the Controlled Polymerization of ε-Caprolactoneen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=44&spage=5133&epage=5140&date=2005&atitle=Carbon-bridge+Bis(phenolato)+Lanthanide+alkoxidex:+syntheses,+structures,+and+their+application+in+the+controlled+polymerization+of+e-Caprolactoneen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic050022s-
dc.identifier.pmid15998042-
dc.identifier.volume44-
dc.identifier.issue14-
dc.identifier.spage5133-
dc.identifier.epage5140-
dc.identifier.isiWOS:000230555400034-
dc.publisher.placeUnited States-

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