Structurally defined zincated and aluminated complexes of ferrocene made by alkali-metal-synergistic syntheses

William Clegg, Elaine Crosbie, Sophie H. Dale-Black, Eva Hevia, Gordon W. Honeyman, Alan R. Kennedy, Robert E. Mulvey, Donna L. Ramsay, Stuart D. Robertson

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Reaction of ferrocene with 1 or 2 molar equiv of the synergistic-operative bimetallic sodium zincate base TMEDA·Na(μ-TMP)(μ-tBu)Zn(tBu) yields mainly mono- or dizincated complexes TMEDA·Na(μ-TMP)[μ-(C5H4)Fe(C5H5)]ZntBu (1) and [TMEDA·Na(μ-TMP)Zn(tBu)]2(C5H4)2Fe (2). Likewise, the separated pairing of Li(TMP) and (TMP)AliBu2 in the presence of THF can mono- or dimetalate ferrocene in a synergistic two-step lithiation/trans-metal-trapping protocol to give THF·Li(μ-TMP)[μ-(C5H4)Fe(C5H5)]Al(iBu)2 (4) or [THF·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (5). In the absence of Lewis donating cosolvents, a 4-fold excess of the sodium zincate appears to produce an unprecedented 4-fold zincated ferrocene of formula Na4(TMP)4Zn4(tBu)4[(C5H3)2Fe] (3), whereas when donor solvent is withheld from the lithium/aluminum pairing, only dimetalation of ferrocene is possible. Tetrametalation seems to be inhibited by the in situ generation of TMP(H) via amido basicity, which then acts as a Lewis donor toward lithium, preventing inverse-crown formation and preferentially forming the Lewis acid–Lewis base adduct [TMP(H)·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (6). With the exception of 3, all aforementioned complexes have been characterized by X-ray crystallography, while 1–6 have also been studied by solution NMR spectroscopic studies.
LanguageEnglish
Pages2580-2589
Number of pages10
JournalOrganometallics
Volume34
Issue number11
Early online date4 Feb 2015
DOIs
Publication statusPublished - 2015

Fingerprint

Thymidine Monophosphate
Alkali Metals
alkali metals
lithium
sodium
Lewis base
synthesis
adducts
crystallography
trapping
aluminum
nuclear magnetic resonance
acids
metals
x rays
Lithium
ferrocene
Sodium
Lewis Bases
Lewis Acids

Keywords

  • ferrocene
  • solvents
  • zinc pairing
  • aluminium pairing
  • Tetrametalation

Cite this

@article{81688af3bed64484b303fde656f79a48,
title = "Structurally defined zincated and aluminated complexes of ferrocene made by alkali-metal-synergistic syntheses",
abstract = "Reaction of ferrocene with 1 or 2 molar equiv of the synergistic-operative bimetallic sodium zincate base TMEDA·Na(μ-TMP)(μ-tBu)Zn(tBu) yields mainly mono- or dizincated complexes TMEDA·Na(μ-TMP)[μ-(C5H4)Fe(C5H5)]ZntBu (1) and [TMEDA·Na(μ-TMP)Zn(tBu)]2(C5H4)2Fe (2). Likewise, the separated pairing of Li(TMP) and (TMP)AliBu2 in the presence of THF can mono- or dimetalate ferrocene in a synergistic two-step lithiation/trans-metal-trapping protocol to give THF·Li(μ-TMP)[μ-(C5H4)Fe(C5H5)]Al(iBu)2 (4) or [THF·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (5). In the absence of Lewis donating cosolvents, a 4-fold excess of the sodium zincate appears to produce an unprecedented 4-fold zincated ferrocene of formula Na4(TMP)4Zn4(tBu)4[(C5H3)2Fe] (3), whereas when donor solvent is withheld from the lithium/aluminum pairing, only dimetalation of ferrocene is possible. Tetrametalation seems to be inhibited by the in situ generation of TMP(H) via amido basicity, which then acts as a Lewis donor toward lithium, preventing inverse-crown formation and preferentially forming the Lewis acid–Lewis base adduct [TMP(H)·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (6). With the exception of 3, all aforementioned complexes have been characterized by X-ray crystallography, while 1–6 have also been studied by solution NMR spectroscopic studies.",
keywords = "ferrocene, solvents, zinc pairing, aluminium pairing, Tetrametalation",
author = "William Clegg and Elaine Crosbie and Dale-Black, {Sophie H.} and Eva Hevia and Honeyman, {Gordon W.} and Kennedy, {Alan R.} and Mulvey, {Robert E.} and Ramsay, {Donna L.} and Robertson, {Stuart D.}",
year = "2015",
doi = "10.1021/om5012352",
language = "English",
volume = "34",
pages = "2580--2589",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "11",

}

Structurally defined zincated and aluminated complexes of ferrocene made by alkali-metal-synergistic syntheses. / Clegg, William; Crosbie, Elaine; Dale-Black, Sophie H.; Hevia, Eva; Honeyman, Gordon W.; Kennedy, Alan R.; Mulvey, Robert E.; Ramsay, Donna L.; Robertson, Stuart D.

In: Organometallics, Vol. 34, No. 11, 2015, p. 2580-2589.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structurally defined zincated and aluminated complexes of ferrocene made by alkali-metal-synergistic syntheses

AU - Clegg, William

AU - Crosbie, Elaine

AU - Dale-Black, Sophie H.

AU - Hevia, Eva

AU - Honeyman, Gordon W.

AU - Kennedy, Alan R.

AU - Mulvey, Robert E.

AU - Ramsay, Donna L.

AU - Robertson, Stuart D.

PY - 2015

Y1 - 2015

N2 - Reaction of ferrocene with 1 or 2 molar equiv of the synergistic-operative bimetallic sodium zincate base TMEDA·Na(μ-TMP)(μ-tBu)Zn(tBu) yields mainly mono- or dizincated complexes TMEDA·Na(μ-TMP)[μ-(C5H4)Fe(C5H5)]ZntBu (1) and [TMEDA·Na(μ-TMP)Zn(tBu)]2(C5H4)2Fe (2). Likewise, the separated pairing of Li(TMP) and (TMP)AliBu2 in the presence of THF can mono- or dimetalate ferrocene in a synergistic two-step lithiation/trans-metal-trapping protocol to give THF·Li(μ-TMP)[μ-(C5H4)Fe(C5H5)]Al(iBu)2 (4) or [THF·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (5). In the absence of Lewis donating cosolvents, a 4-fold excess of the sodium zincate appears to produce an unprecedented 4-fold zincated ferrocene of formula Na4(TMP)4Zn4(tBu)4[(C5H3)2Fe] (3), whereas when donor solvent is withheld from the lithium/aluminum pairing, only dimetalation of ferrocene is possible. Tetrametalation seems to be inhibited by the in situ generation of TMP(H) via amido basicity, which then acts as a Lewis donor toward lithium, preventing inverse-crown formation and preferentially forming the Lewis acid–Lewis base adduct [TMP(H)·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (6). With the exception of 3, all aforementioned complexes have been characterized by X-ray crystallography, while 1–6 have also been studied by solution NMR spectroscopic studies.

AB - Reaction of ferrocene with 1 or 2 molar equiv of the synergistic-operative bimetallic sodium zincate base TMEDA·Na(μ-TMP)(μ-tBu)Zn(tBu) yields mainly mono- or dizincated complexes TMEDA·Na(μ-TMP)[μ-(C5H4)Fe(C5H5)]ZntBu (1) and [TMEDA·Na(μ-TMP)Zn(tBu)]2(C5H4)2Fe (2). Likewise, the separated pairing of Li(TMP) and (TMP)AliBu2 in the presence of THF can mono- or dimetalate ferrocene in a synergistic two-step lithiation/trans-metal-trapping protocol to give THF·Li(μ-TMP)[μ-(C5H4)Fe(C5H5)]Al(iBu)2 (4) or [THF·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (5). In the absence of Lewis donating cosolvents, a 4-fold excess of the sodium zincate appears to produce an unprecedented 4-fold zincated ferrocene of formula Na4(TMP)4Zn4(tBu)4[(C5H3)2Fe] (3), whereas when donor solvent is withheld from the lithium/aluminum pairing, only dimetalation of ferrocene is possible. Tetrametalation seems to be inhibited by the in situ generation of TMP(H) via amido basicity, which then acts as a Lewis donor toward lithium, preventing inverse-crown formation and preferentially forming the Lewis acid–Lewis base adduct [TMP(H)·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (6). With the exception of 3, all aforementioned complexes have been characterized by X-ray crystallography, while 1–6 have also been studied by solution NMR spectroscopic studies.

KW - ferrocene

KW - solvents

KW - zinc pairing

KW - aluminium pairing

KW - Tetrametalation

U2 - 10.1021/om5012352

DO - 10.1021/om5012352

M3 - Article

VL - 34

SP - 2580

EP - 2589

JO - Organometallics

T2 - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 11

ER -