Structural and magnetic insights into the trinuclear ferrocenophane and unexpected hydrido inverse crown products of alkali-metal-mediated manganation(ii) of ferrocene

V.L. Blair, L.M. Carrella, W. Clegg, J. Klett, R.E. Mulvey, E. Rentschler, L. Russo

Research output: Contribution to journalArticle

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Abstract

With the aim of introducing the diisopropylamide [NiPr2]- ligand to alkali-metal-mediated manganation (AMMMn) chemistry, the temperature-dependent reactions of a 1:1:3 mixture of butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, the reaction affords the surprising, ferrocene-free, hydrido product [Na2Mn2 (-H)2{N(iPr)2}4]2 toluene (1), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces 1 in an isolated crystalline yield of 62 %. At lower temperatures, the same bimetallic amide mixture leads to the manganation of ferrocene to generate the first trimanganese, trinuclear ferrocenophane, [{Fe(C5H4)2}3{Mn3Na2(NiPr2)2 (HNiPr2)2}] (2) in an isolated crystalline yield of 81 %. Both 1 and 2 have been characterised by X-ray crystallographic studies. The magnetic properties of paramagnetic 1 and 2 have also been examined by variable-temperature magnetisation measurements on powdered samples. For 1, the room-temperature value for T is 3.45 cm3 K mol-1, and on lowering the temperature a strong antiferromagnetic coupling between the two Mn ions is observed. For 2, the room-temperature value for T is 4.06 cm3 K mol-1, which is significantly lower than the expected value for three isolated paramagnetic MnII ions.
LanguageEnglish
Pages856-863
Number of pages8
JournalChemistry - A European Journal
Volume15
Issue number4
DOIs
Publication statusPublished - 12 Jan 2009

Fingerprint

Alkali Metals
Temperature
Toluene
Ions
Crystalline materials
Hexanes
Manganese
ferrocene
Amides
Magnetization
Magnetic properties
Ligands
X rays

Keywords

  • hydrides
  • inverse crown compounds
  • magnetic properties
  • manganese
  • metalation
  • sodium

Cite this

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title = "Structural and magnetic insights into the trinuclear ferrocenophane and unexpected hydrido inverse crown products of alkali-metal-mediated manganation(ii) of ferrocene",
abstract = "With the aim of introducing the diisopropylamide [NiPr2]- ligand to alkali-metal-mediated manganation (AMMMn) chemistry, the temperature-dependent reactions of a 1:1:3 mixture of butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, the reaction affords the surprising, ferrocene-free, hydrido product [Na2Mn2 (-H)2{N(iPr)2}4]2 toluene (1), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces 1 in an isolated crystalline yield of 62 {\%}. At lower temperatures, the same bimetallic amide mixture leads to the manganation of ferrocene to generate the first trimanganese, trinuclear ferrocenophane, [{Fe(C5H4)2}3{Mn3Na2(NiPr2)2 (HNiPr2)2}] (2) in an isolated crystalline yield of 81 {\%}. Both 1 and 2 have been characterised by X-ray crystallographic studies. The magnetic properties of paramagnetic 1 and 2 have also been examined by variable-temperature magnetisation measurements on powdered samples. For 1, the room-temperature value for T is 3.45 cm3 K mol-1, and on lowering the temperature a strong antiferromagnetic coupling between the two Mn ions is observed. For 2, the room-temperature value for T is 4.06 cm3 K mol-1, which is significantly lower than the expected value for three isolated paramagnetic MnII ions.",
keywords = "hydrides, inverse crown compounds, magnetic properties, manganese, metalation, sodium",
author = "V.L. Blair and L.M. Carrella and W. Clegg and J. Klett and R.E. Mulvey and E. Rentschler and L. Russo",
year = "2009",
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Structural and magnetic insights into the trinuclear ferrocenophane and unexpected hydrido inverse crown products of alkali-metal-mediated manganation(ii) of ferrocene. / Blair, V.L.; Carrella, L.M.; Clegg, W.; Klett, J.; Mulvey, R.E.; Rentschler, E.; Russo, L.

In: Chemistry - A European Journal, Vol. 15, No. 4, 12.01.2009, p. 856-863.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structural and magnetic insights into the trinuclear ferrocenophane and unexpected hydrido inverse crown products of alkali-metal-mediated manganation(ii) of ferrocene

AU - Blair, V.L.

AU - Carrella, L.M.

AU - Clegg, W.

AU - Klett, J.

AU - Mulvey, R.E.

AU - Rentschler, E.

AU - Russo, L.

PY - 2009/1/12

Y1 - 2009/1/12

N2 - With the aim of introducing the diisopropylamide [NiPr2]- ligand to alkali-metal-mediated manganation (AMMMn) chemistry, the temperature-dependent reactions of a 1:1:3 mixture of butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, the reaction affords the surprising, ferrocene-free, hydrido product [Na2Mn2 (-H)2{N(iPr)2}4]2 toluene (1), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces 1 in an isolated crystalline yield of 62 %. At lower temperatures, the same bimetallic amide mixture leads to the manganation of ferrocene to generate the first trimanganese, trinuclear ferrocenophane, [{Fe(C5H4)2}3{Mn3Na2(NiPr2)2 (HNiPr2)2}] (2) in an isolated crystalline yield of 81 %. Both 1 and 2 have been characterised by X-ray crystallographic studies. The magnetic properties of paramagnetic 1 and 2 have also been examined by variable-temperature magnetisation measurements on powdered samples. For 1, the room-temperature value for T is 3.45 cm3 K mol-1, and on lowering the temperature a strong antiferromagnetic coupling between the two Mn ions is observed. For 2, the room-temperature value for T is 4.06 cm3 K mol-1, which is significantly lower than the expected value for three isolated paramagnetic MnII ions.

AB - With the aim of introducing the diisopropylamide [NiPr2]- ligand to alkali-metal-mediated manganation (AMMMn) chemistry, the temperature-dependent reactions of a 1:1:3 mixture of butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, the reaction affords the surprising, ferrocene-free, hydrido product [Na2Mn2 (-H)2{N(iPr)2}4]2 toluene (1), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces 1 in an isolated crystalline yield of 62 %. At lower temperatures, the same bimetallic amide mixture leads to the manganation of ferrocene to generate the first trimanganese, trinuclear ferrocenophane, [{Fe(C5H4)2}3{Mn3Na2(NiPr2)2 (HNiPr2)2}] (2) in an isolated crystalline yield of 81 %. Both 1 and 2 have been characterised by X-ray crystallographic studies. The magnetic properties of paramagnetic 1 and 2 have also been examined by variable-temperature magnetisation measurements on powdered samples. For 1, the room-temperature value for T is 3.45 cm3 K mol-1, and on lowering the temperature a strong antiferromagnetic coupling between the two Mn ions is observed. For 2, the room-temperature value for T is 4.06 cm3 K mol-1, which is significantly lower than the expected value for three isolated paramagnetic MnII ions.

KW - hydrides

KW - inverse crown compounds

KW - magnetic properties

KW - manganese

KW - metalation

KW - sodium

U2 - 10.1002/chem.200802086

DO - 10.1002/chem.200802086

M3 - Article

VL - 15

SP - 856

EP - 863

JO - Chemistry - A European Journal

T2 - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 4

ER -