Dendritic lanthanide complexes and the effect of Lewis-acid encapsulation

D L  Stone; G M  Dykes; D K  Smith

doi:10.1039/b309643b

Dendritic lanthanide complexes and the effect of Lewis-acid encapsulation

D L Stone, G M Dykes, D K Smith

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The synthesis of complexes using terbium(III) ions and dendritic branches based on L-lysine building blocks is reported. These complexes are bound via predominantly electrostatic lanthanide-carboxylate interactions, and were characterised using a range of approaches. The ability of these Lewis-acidic complexes and terbium acetate to influence the regiochemical outcome of a Diels-Alder reaction was investigated, but they were found to have minimal effect. Interestingly, however, non-dendritic terbium(III) acetate was observed to remain bound to the product of the reaction, broadening its NMR spectrum, whilst the dendritic terbium complexes did not interact in this way. This indicates that the Lewis-acidic centre in the more highly functionalised dendritic derivatives may be inaccessible, either sterically or electronically, both to substrates and products of organic transformations.

Original language	English
Pages (from-to)	3902-3906
Number of pages	5
Journal	Dalton Transactions
Issue number	20
DOIs	https://doi.org/10.1039/b309643b
Publication status	Published - 2003

Keywords

BRANCHED FERROCENE DERIVATIVES
ASYMMETRIC CATALYSIS
SITE-ISOLATION
ENANTIOSELECTIVE CATALYSIS
PHOTOPHYSICAL PROPERTIES
ELECTRON-TRANSFER
CORE DENDRIMERS
HENRY REACTION
LUMINESCENCE
LIGANDS

Access to Document

10.1039/b309643b

Cite this

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title = "Dendritic lanthanide complexes and the effect of Lewis-acid encapsulation",

abstract = "The synthesis of complexes using terbium(III) ions and dendritic branches based on L-lysine building blocks is reported. These complexes are bound via predominantly electrostatic lanthanide-carboxylate interactions, and were characterised using a range of approaches. The ability of these Lewis-acidic complexes and terbium acetate to influence the regiochemical outcome of a Diels-Alder reaction was investigated, but they were found to have minimal effect. Interestingly, however, non-dendritic terbium(III) acetate was observed to remain bound to the product of the reaction, broadening its NMR spectrum, whilst the dendritic terbium complexes did not interact in this way. This indicates that the Lewis-acidic centre in the more highly functionalised dendritic derivatives may be inaccessible, either sterically or electronically, both to substrates and products of organic transformations.",

keywords = "BRANCHED FERROCENE DERIVATIVES, ASYMMETRIC CATALYSIS, SITE-ISOLATION, ENANTIOSELECTIVE CATALYSIS, PHOTOPHYSICAL PROPERTIES, ELECTRON-TRANSFER, CORE DENDRIMERS, HENRY REACTION, LUMINESCENCE, LIGANDS",

author = "Stone, {D L} and Dykes, {G M} and Smith, {D K}",

year = "2003",

doi = "10.1039/b309643b",

language = "English",

pages = "3902--3906",

journal = "Dalton Transactions",

issn = "1477-9234",

publisher = "The Royal Society of Chemistry",

number = "20",

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TY - JOUR

T1 - Dendritic lanthanide complexes and the effect of Lewis-acid encapsulation

AU - Stone, D L

AU - Dykes, G M

AU - Smith, D K

PY - 2003

Y1 - 2003

N2 - The synthesis of complexes using terbium(III) ions and dendritic branches based on L-lysine building blocks is reported. These complexes are bound via predominantly electrostatic lanthanide-carboxylate interactions, and were characterised using a range of approaches. The ability of these Lewis-acidic complexes and terbium acetate to influence the regiochemical outcome of a Diels-Alder reaction was investigated, but they were found to have minimal effect. Interestingly, however, non-dendritic terbium(III) acetate was observed to remain bound to the product of the reaction, broadening its NMR spectrum, whilst the dendritic terbium complexes did not interact in this way. This indicates that the Lewis-acidic centre in the more highly functionalised dendritic derivatives may be inaccessible, either sterically or electronically, both to substrates and products of organic transformations.

AB - The synthesis of complexes using terbium(III) ions and dendritic branches based on L-lysine building blocks is reported. These complexes are bound via predominantly electrostatic lanthanide-carboxylate interactions, and were characterised using a range of approaches. The ability of these Lewis-acidic complexes and terbium acetate to influence the regiochemical outcome of a Diels-Alder reaction was investigated, but they were found to have minimal effect. Interestingly, however, non-dendritic terbium(III) acetate was observed to remain bound to the product of the reaction, broadening its NMR spectrum, whilst the dendritic terbium complexes did not interact in this way. This indicates that the Lewis-acidic centre in the more highly functionalised dendritic derivatives may be inaccessible, either sterically or electronically, both to substrates and products of organic transformations.

KW - BRANCHED FERROCENE DERIVATIVES

KW - ASYMMETRIC CATALYSIS

KW - SITE-ISOLATION

KW - ENANTIOSELECTIVE CATALYSIS

KW - PHOTOPHYSICAL PROPERTIES

KW - ELECTRON-TRANSFER

KW - CORE DENDRIMERS

KW - HENRY REACTION

KW - LUMINESCENCE

KW - LIGANDS

U2 - 10.1039/b309643b

DO - 10.1039/b309643b

M3 - Article

SN - 1477-9234

SP - 3902

EP - 3906

JO - Dalton Transactions

JF - Dalton Transactions

IS - 20

ER -