Accessible heavier s-block dihydropyridines: structural elucidation and reactivity of isolable molecular hydride sources

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Abstract

The straightforward metathesis of 1-lithio-2-tbutyl-1,2-dihydropyridine using metal tert-butoxide (Na/K) has resulted in the first preparation and isolation of a series of heavier alkali metal dihydropyridines. By employing donors, TMEDA, PMDETA and THF, five new metallodihydropyridine compounds were isolated and fully characterised. Three distinct structural motifs have been observed; a dimer, a dimer of dimers and a novel polymeric dihydropyridylpotassium compound, and the influence of cation π-interactions therein has been discussed. Thermal volatility analysis has shown that these complexes have the potential to be used as simple isolable sodium or potassium hydride surrogates, which is confirmed in test reactions with benzophenone.
LanguageEnglish
Pages6234-6240
Number of pages7
JournalDalton Transactions
Volume45
Issue number14
Early online date7 Dec 2015
DOIs
Publication statusPublished - 14 Apr 2016

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Dihydropyridines
Hydrides
Dimers
Alkali Metals
Thermoanalysis
Heavy metals
Cations
Potassium
Metals
Sodium

Keywords

  • dihydropyridines
  • DHP chemistry
  • metallodihydropyridine

Cite this

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title = "Accessible heavier s-block dihydropyridines: structural elucidation and reactivity of isolable molecular hydride sources",
abstract = "The straightforward metathesis of 1-lithio-2-tbutyl-1,2-dihydropyridine using metal tert-butoxide (Na/K) has resulted in the first preparation and isolation of a series of heavier alkali metal dihydropyridines. By employing donors, TMEDA, PMDETA and THF, five new metallodihydropyridine compounds were isolated and fully characterised. Three distinct structural motifs have been observed; a dimer, a dimer of dimers and a novel polymeric dihydropyridylpotassium compound, and the influence of cation π-interactions therein has been discussed. Thermal volatility analysis has shown that these complexes have the potential to be used as simple isolable sodium or potassium hydride surrogates, which is confirmed in test reactions with benzophenone.",
keywords = "dihydropyridines, DHP chemistry, metallodihydropyridine",
author = "Orr, {Samantha A.} and Kennedy, {Alan R.} and Liggat, {John J.} and Ross McLellan and Mulvey, {Robert E.} and Robertson, {Stuart D.}",
year = "2016",
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day = "14",
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language = "English",
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T1 - Accessible heavier s-block dihydropyridines

T2 - Dalton Transactions

AU - Orr, Samantha A.

AU - Kennedy, Alan R.

AU - Liggat, John J.

AU - McLellan, Ross

AU - Mulvey, Robert E.

AU - Robertson, Stuart D.

PY - 2016/4/14

Y1 - 2016/4/14

N2 - The straightforward metathesis of 1-lithio-2-tbutyl-1,2-dihydropyridine using metal tert-butoxide (Na/K) has resulted in the first preparation and isolation of a series of heavier alkali metal dihydropyridines. By employing donors, TMEDA, PMDETA and THF, five new metallodihydropyridine compounds were isolated and fully characterised. Three distinct structural motifs have been observed; a dimer, a dimer of dimers and a novel polymeric dihydropyridylpotassium compound, and the influence of cation π-interactions therein has been discussed. Thermal volatility analysis has shown that these complexes have the potential to be used as simple isolable sodium or potassium hydride surrogates, which is confirmed in test reactions with benzophenone.

AB - The straightforward metathesis of 1-lithio-2-tbutyl-1,2-dihydropyridine using metal tert-butoxide (Na/K) has resulted in the first preparation and isolation of a series of heavier alkali metal dihydropyridines. By employing donors, TMEDA, PMDETA and THF, five new metallodihydropyridine compounds were isolated and fully characterised. Three distinct structural motifs have been observed; a dimer, a dimer of dimers and a novel polymeric dihydropyridylpotassium compound, and the influence of cation π-interactions therein has been discussed. Thermal volatility analysis has shown that these complexes have the potential to be used as simple isolable sodium or potassium hydride surrogates, which is confirmed in test reactions with benzophenone.

KW - dihydropyridines

KW - DHP chemistry

KW - metallodihydropyridine

UR - http://pubs.rsc.org/en/journals/journalissues/dt#!recentarticles&adv

U2 - 10.1039/C5DT04224K

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