A homologous series of regioselectively tetradeprotonated group 8 metallocenes: New inverse crown ring compounds synthesized via a mixed sodium-magnesium tris(diisopropylamide) synergic base

Prokopis C. Andrikopoulos, David R. Armstrong, William Clegg, Carly J. Gilfillan, Eva Hevia, Alan R. Kennedy, Robert E. Mulvey, Charles T. O'Hara, John A. Parkinson, Duncan M. Tooke

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Abstract

Subjecting ferrocene, ruthenocene, or osmocene to the synergic amide base sodium-magnesium tris(diisopropylamido) affords a unique homologous series of metallocene derivatives of general formula [{M(C5H3)(2)}Na4Mg4(i-Pr2N)(8)] (where M = Fe (1), Ru (2), or Os (3)). X-ray crystallographic studies of 1-3 reveal a common molecular 'inverse crown' structure comprising a 16-membered [(NaNMgN)(4)](4+) 'host' ring and a metallocenetetraide [M(C5H3)(2)](4-) 'guest' core, the cleaved protons of which are lost selectively from the 1, 1', 3, and 3'-positions. Variable-temperature NMR spectroscopic studies indicate that 1, 2, and 3 each exist as two distinct interconverting conformers in arene solution, the rates of exchange of which have been calculated using coalescence and EXSY NMR measurements.
LanguageEnglish
Pages11612-11620
Number of pages8
JournalJournal of the American Chemical Society
Volume126
Issue number37
Early online date26 Aug 2004
DOIs
Publication statusPublished - 22 Sep 2004

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Crown Compounds
Organometallics
Crowns
Amides
Magnesium
Protons
Sodium
Nuclear magnetic resonance
X-Rays
Temperature
Coalescence
Ion exchange
Derivatives
X rays
ruthenocene
osmocene
metallocene
ferrocene

Keywords

  • alkali metal-magnesium
  • molecular-orbital methods
  • gaussian-type basis
  • organic-molecules
  • crystal-structure
  • ferrocene
  • chemistry
  • complexes
  • block
  • mercuracarborands

Cite this

@article{890041e2b1764090a3120a14a6da9804,
title = "A homologous series of regioselectively tetradeprotonated group 8 metallocenes: New inverse crown ring compounds synthesized via a mixed sodium-magnesium tris(diisopropylamide) synergic base",
abstract = "Subjecting ferrocene, ruthenocene, or osmocene to the synergic amide base sodium-magnesium tris(diisopropylamido) affords a unique homologous series of metallocene derivatives of general formula [{M(C5H3)(2)}Na4Mg4(i-Pr2N)(8)] (where M = Fe (1), Ru (2), or Os (3)). X-ray crystallographic studies of 1-3 reveal a common molecular 'inverse crown' structure comprising a 16-membered [(NaNMgN)(4)](4+) 'host' ring and a metallocenetetraide [M(C5H3)(2)](4-) 'guest' core, the cleaved protons of which are lost selectively from the 1, 1', 3, and 3'-positions. Variable-temperature NMR spectroscopic studies indicate that 1, 2, and 3 each exist as two distinct interconverting conformers in arene solution, the rates of exchange of which have been calculated using coalescence and EXSY NMR measurements.",
keywords = "alkali metal-magnesium, molecular-orbital methods, gaussian-type basis, organic-molecules, crystal-structure, ferrocene, chemistry, complexes, block, mercuracarborands",
author = "Andrikopoulos, {Prokopis C.} and Armstrong, {David R.} and William Clegg and Gilfillan, {Carly J.} and Eva Hevia and Kennedy, {Alan R.} and Mulvey, {Robert E.} and O'Hara, {Charles T.} and Parkinson, {John A.} and Tooke, {Duncan M.}",
year = "2004",
month = "9",
day = "22",
doi = "10.1021/ja0472230",
language = "English",
volume = "126",
pages = "11612--11620",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
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TY - JOUR

T1 - A homologous series of regioselectively tetradeprotonated group 8 metallocenes: New inverse crown ring compounds synthesized via a mixed sodium-magnesium tris(diisopropylamide) synergic base

AU - Andrikopoulos, Prokopis C.

AU - Armstrong, David R.

AU - Clegg, William

AU - Gilfillan, Carly J.

AU - Hevia, Eva

AU - Kennedy, Alan R.

AU - Mulvey, Robert E.

AU - O'Hara, Charles T.

AU - Parkinson, John A.

AU - Tooke, Duncan M.

PY - 2004/9/22

Y1 - 2004/9/22

N2 - Subjecting ferrocene, ruthenocene, or osmocene to the synergic amide base sodium-magnesium tris(diisopropylamido) affords a unique homologous series of metallocene derivatives of general formula [{M(C5H3)(2)}Na4Mg4(i-Pr2N)(8)] (where M = Fe (1), Ru (2), or Os (3)). X-ray crystallographic studies of 1-3 reveal a common molecular 'inverse crown' structure comprising a 16-membered [(NaNMgN)(4)](4+) 'host' ring and a metallocenetetraide [M(C5H3)(2)](4-) 'guest' core, the cleaved protons of which are lost selectively from the 1, 1', 3, and 3'-positions. Variable-temperature NMR spectroscopic studies indicate that 1, 2, and 3 each exist as two distinct interconverting conformers in arene solution, the rates of exchange of which have been calculated using coalescence and EXSY NMR measurements.

AB - Subjecting ferrocene, ruthenocene, or osmocene to the synergic amide base sodium-magnesium tris(diisopropylamido) affords a unique homologous series of metallocene derivatives of general formula [{M(C5H3)(2)}Na4Mg4(i-Pr2N)(8)] (where M = Fe (1), Ru (2), or Os (3)). X-ray crystallographic studies of 1-3 reveal a common molecular 'inverse crown' structure comprising a 16-membered [(NaNMgN)(4)](4+) 'host' ring and a metallocenetetraide [M(C5H3)(2)](4-) 'guest' core, the cleaved protons of which are lost selectively from the 1, 1', 3, and 3'-positions. Variable-temperature NMR spectroscopic studies indicate that 1, 2, and 3 each exist as two distinct interconverting conformers in arene solution, the rates of exchange of which have been calculated using coalescence and EXSY NMR measurements.

KW - alkali metal-magnesium

KW - molecular-orbital methods

KW - gaussian-type basis

KW - organic-molecules

KW - crystal-structure

KW - ferrocene

KW - chemistry

KW - complexes

KW - block

KW - mercuracarborands

UR - http://pubs.acs.org/cgi-bin/article.cgi/jacsat/2004/126/i37/pdf/ja0472230.pdf

U2 - 10.1021/ja0472230

DO - 10.1021/ja0472230

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SP - 11612

EP - 11620

JO - Journal of the American Chemical Society

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JF - Journal of the American Chemical Society

SN - 0002-7863

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