Synthesis, Characterisation of Carbon‐Bridged (Diphenolato)lanthanide Complexes and Their Catalytic Activity for Diels–Alder Reactions
- 1 February 2005
- journal article
- research article
- Published by Wiley in European Journal of Inorganic Chemistry
- Vol. 2005 (4) , 676-684
- https://doi.org/10.1002/ejic.200400519
Abstract
The synthesis and structures of new lanthanide complexes supported by the carbon‐bridged diphenolato ligand 2,2′‐methylenebis(6‐tert‐butyl‐4‐methylphenolato) (MBMP2–) are described. Reactions of anhydrous lanthanide trichlorides with Na2MBMP in a 1:2 molar ratio in THF at room temperature afforded the corresponding “ate” (diphenolato)lanthanide complexes [(THF)nLn(MBMP)2Na(THF)2] [Ln = Nd (1), Sm (2),n= 2; Ln = Yb,n= 1 (3)]. Recrystallisation of complexes1–3from toluene in the presence of DME gave the discrete ion‐pair complexes [(MBMP)2Ln(THF)2][Na(DME)2(THF)2] [Ln = Nd (4), Sm (5), Yb (6)]. These complexes have been fully characterised. The single‐crystal structural analyses of1,3and6revealed that the coordination geometries of the lanthanide ions can be best described as distorted octahedral in complexes1and6and distorted trigonal‐bipyramidal in complex3. It was found that these lanthanide complexes are able to act as Lewis acids to catalyse the Diels–Alder reactions of cyclopentadiene with substituted dienophiles with good activity and stereoselectivity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)Keywords
This publication has 68 references indexed in Scilit:
- Novel lanthanide(ii) complexes supported by carbon-bridged biphenolate ligands: synthesis, structure and catalytic activityDalton Transactions, 2004
- Rare earth metal complexes supported by 1,ω-dithiaalkanediyl-bridged bis(phenolato) ligands: synthesis, characterization and ring-opening polymerization catalysis ofl-lactideDalton Transactions, 2003
- Monocyclopentadienyl and ansa-Monocyclopentadienylalkoxo Complexes of Titanium Containing the 2,2‘-Methylenebis(6-tert-butyl-4-methylphenoxo) Ligand. Synthesis, Characterization, and Polymerization Catalyst Behavior. Molecular Structure of Ti(η5-C5H5)(η2-MBMP)Cl, Ti(η5-C5Me5)(η2-MBMP)Cl, and Ti(η5-C5H4SiMe2-η1-MBMP)Cl2Organometallics, 2003
- Efficient polymerization of acrylonitrile catalyzed by divalent lanthanide complex/ sodium phenolate systemsChinese Science Bulletin, 2001
- Rare Earth Complexes of Bulky 2,6-Diphenylphenolates Containing Additional, Potentially Buttressing 3,5-SubstituentsEuropean Journal of Inorganic Chemistry, 2001
- Bis(oxazoline) and Bis(oxazolinyl)pyridine Copper Complexes as Enantioselective Diels−Alder Catalysts: Reaction Scope and Synthetic ApplicationsJournal of the American Chemical Society, 1999
- Organoamido‐ and Aryloxo‐Lanthanoids, 17 Novel Low‐Coordinate Lanthanoid (II) and ‐(III) Aryloxide Complexes ‐ the X‐ray Structures of Bis (2,6‐diphenylphenolato) tris(tetrahydrofuran)‐ytterbium (II), Bis(1,2‐dimethoxyethane)bis(2,6‐diphenylphenolato)ytterbium(II),‐neodymium(III)European Journal of Inorganic Chemistry, 1997
- Effect of microemulsions on the Diels-Alder reaction: endo/exo ratios in the reaction of cyclopentadiene and methyl methacrylateThe Journal of Organic Chemistry, 1982
- Synthesis and crystallographic characterization of a dimeric alkynide-bridged organolanthanide: [(C5H5)2ErC.ident.CC(CH3)3]2Inorganic Chemistry, 1981
- Preparation of anhydrous lanthanide halides, especially iodidesJournal of Inorganic and Nuclear Chemistry, 1962