Structural elucidation of homometallic anthracenolates synthesised via deprotonative metallation of anthrone

William Clegg, Ben J. Fleming, Pablo Garcia-Alvarez, Lorna M. Hogg, Alan R. Kennedy, Jan Klett, Antonio J. Martinez-Martinez, Robert E. Mulvey, Luca Russo, Charles T. O'Hara

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Five novel neutral homometallic complexes which contain the anthracen-9-olate anion have been prepared and characterised by treating anthrone with an organometallic base to induce aromatisation. Three of these complexes [(donor)center dot M(OC14H9)](2) (2-4) are dimeric and contain sodium, lithium and potassium respectively. For 2 and 3 the donor is N,N,N',N'-tetramethylethylenediamine (TMEDA) whilst for 4 it is N, N, N', N '', N ''-pentamethyldiethylenetriamine (PMDETA). When bimetallic reagents such as [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] are employed, only the alkali-metal-containing species is isolated (e.g., 2 in this case). Providing a contrast, complexes 5 [(TMEDA)center dot Mg(OC14H9)Bu-n] and 6 [(TMEDA)center dot Zn(OC14H9)Et] are monomeric. The alkali metal complexes were prepared by reacting anthrone with one molar equivalent of either n-butylsodium, n-butyllithium or (trimethylsilyl)methylpotassium in the presence of the required donor solvent. For 5 and 6, equimolar quantities of di-n-butylmagnesium and diethylzinc, respectively, were reacted with anthrone in the presence of TMEDA. The solid-state structures and the arene solution structures of 2-6 have been determined by X-ray crystallography and NMR spectroscopy respectively.

LanguageEnglish
Pages2512-2519
Number of pages8
JournalDalton Transactions
Volume42
Issue number7
Early online date22 Nov 2012
DOIs
Publication statusPublished - 2013

Fingerprint

Alkali Metals
Aromatization
X ray crystallography
Coordination Complexes
Organometallics
Lithium
Nuclear magnetic resonance spectroscopy
Anions
Potassium
Sodium
N,N,N',N'-tetramethylethylenediamine
anthrone
n-butyllithium
Na(mu-(t)Bu)(mu-TMP)Zn((t)Bu)
N,N,N',N'',N''-pentamethyldiethylenetriamine
diethylzinc

Keywords

  • structural elucidation
  • homometallic anthracenolates
  • deprotonative
  • metallation
  • anthrone
  • synthesis

Cite this

Clegg, William ; Fleming, Ben J. ; Garcia-Alvarez, Pablo ; Hogg, Lorna M. ; Kennedy, Alan R. ; Klett, Jan ; Martinez-Martinez, Antonio J. ; Mulvey, Robert E. ; Russo, Luca ; O'Hara, Charles T. / Structural elucidation of homometallic anthracenolates synthesised via deprotonative metallation of anthrone. In: Dalton Transactions. 2013 ; Vol. 42, No. 7. pp. 2512-2519.
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abstract = "Five novel neutral homometallic complexes which contain the anthracen-9-olate anion have been prepared and characterised by treating anthrone with an organometallic base to induce aromatisation. Three of these complexes [(donor)center dot M(OC14H9)](2) (2-4) are dimeric and contain sodium, lithium and potassium respectively. For 2 and 3 the donor is N,N,N',N'-tetramethylethylenediamine (TMEDA) whilst for 4 it is N, N, N', N '', N ''-pentamethyldiethylenetriamine (PMDETA). When bimetallic reagents such as [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] are employed, only the alkali-metal-containing species is isolated (e.g., 2 in this case). Providing a contrast, complexes 5 [(TMEDA)center dot Mg(OC14H9)Bu-n] and 6 [(TMEDA)center dot Zn(OC14H9)Et] are monomeric. The alkali metal complexes were prepared by reacting anthrone with one molar equivalent of either n-butylsodium, n-butyllithium or (trimethylsilyl)methylpotassium in the presence of the required donor solvent. For 5 and 6, equimolar quantities of di-n-butylmagnesium and diethylzinc, respectively, were reacted with anthrone in the presence of TMEDA. The solid-state structures and the arene solution structures of 2-6 have been determined by X-ray crystallography and NMR spectroscopy respectively.",
keywords = "structural elucidation, homometallic anthracenolates, deprotonative , metallation , anthrone, synthesis",
author = "William Clegg and Fleming, {Ben J.} and Pablo Garcia-Alvarez and Hogg, {Lorna M.} and Kennedy, {Alan R.} and Jan Klett and Martinez-Martinez, {Antonio J.} and Mulvey, {Robert E.} and Luca Russo and O'Hara, {Charles T.}",
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Clegg, W, Fleming, BJ, Garcia-Alvarez, P, Hogg, LM, Kennedy, AR, Klett, J, Martinez-Martinez, AJ, Mulvey, RE, Russo, L & O'Hara, CT 2013, 'Structural elucidation of homometallic anthracenolates synthesised via deprotonative metallation of anthrone' Dalton Transactions, vol. 42, no. 7, pp. 2512-2519. https://doi.org/10.1039/c2dt32176a

Structural elucidation of homometallic anthracenolates synthesised via deprotonative metallation of anthrone. / Clegg, William; Fleming, Ben J.; Garcia-Alvarez, Pablo; Hogg, Lorna M.; Kennedy, Alan R.; Klett, Jan; Martinez-Martinez, Antonio J.; Mulvey, Robert E.; Russo, Luca; O'Hara, Charles T.

In: Dalton Transactions, Vol. 42, No. 7, 2013, p. 2512-2519.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structural elucidation of homometallic anthracenolates synthesised via deprotonative metallation of anthrone

AU - Clegg, William

AU - Fleming, Ben J.

AU - Garcia-Alvarez, Pablo

AU - Hogg, Lorna M.

AU - Kennedy, Alan R.

AU - Klett, Jan

AU - Martinez-Martinez, Antonio J.

AU - Mulvey, Robert E.

AU - Russo, Luca

AU - O'Hara, Charles T.

PY - 2013

Y1 - 2013

N2 - Five novel neutral homometallic complexes which contain the anthracen-9-olate anion have been prepared and characterised by treating anthrone with an organometallic base to induce aromatisation. Three of these complexes [(donor)center dot M(OC14H9)](2) (2-4) are dimeric and contain sodium, lithium and potassium respectively. For 2 and 3 the donor is N,N,N',N'-tetramethylethylenediamine (TMEDA) whilst for 4 it is N, N, N', N '', N ''-pentamethyldiethylenetriamine (PMDETA). When bimetallic reagents such as [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] are employed, only the alkali-metal-containing species is isolated (e.g., 2 in this case). Providing a contrast, complexes 5 [(TMEDA)center dot Mg(OC14H9)Bu-n] and 6 [(TMEDA)center dot Zn(OC14H9)Et] are monomeric. The alkali metal complexes were prepared by reacting anthrone with one molar equivalent of either n-butylsodium, n-butyllithium or (trimethylsilyl)methylpotassium in the presence of the required donor solvent. For 5 and 6, equimolar quantities of di-n-butylmagnesium and diethylzinc, respectively, were reacted with anthrone in the presence of TMEDA. The solid-state structures and the arene solution structures of 2-6 have been determined by X-ray crystallography and NMR spectroscopy respectively.

AB - Five novel neutral homometallic complexes which contain the anthracen-9-olate anion have been prepared and characterised by treating anthrone with an organometallic base to induce aromatisation. Three of these complexes [(donor)center dot M(OC14H9)](2) (2-4) are dimeric and contain sodium, lithium and potassium respectively. For 2 and 3 the donor is N,N,N',N'-tetramethylethylenediamine (TMEDA) whilst for 4 it is N, N, N', N '', N ''-pentamethyldiethylenetriamine (PMDETA). When bimetallic reagents such as [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] are employed, only the alkali-metal-containing species is isolated (e.g., 2 in this case). Providing a contrast, complexes 5 [(TMEDA)center dot Mg(OC14H9)Bu-n] and 6 [(TMEDA)center dot Zn(OC14H9)Et] are monomeric. The alkali metal complexes were prepared by reacting anthrone with one molar equivalent of either n-butylsodium, n-butyllithium or (trimethylsilyl)methylpotassium in the presence of the required donor solvent. For 5 and 6, equimolar quantities of di-n-butylmagnesium and diethylzinc, respectively, were reacted with anthrone in the presence of TMEDA. The solid-state structures and the arene solution structures of 2-6 have been determined by X-ray crystallography and NMR spectroscopy respectively.

KW - structural elucidation

KW - homometallic anthracenolates

KW - deprotonative

KW - metallation

KW - anthrone

KW - synthesis

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