Structural and Magnetic Insights into the Trinuclear Ferrocenophane and Unexpected Hydrido Inverse Crown Products of Alkali-Metal-Mediated Manganation(II) of Ferrocene

Publication type:
Journal article
Metadata:
Autoren
  • Victoria L Blair
  • Luca M Carrella
  • William Clegg
  • Jan Klett
  • Robert E Mulvey
  • Eva Rentschler
  • Luca Russo
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000262886800007&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/chem.200802086
eISSN
1521-3765
Externe Identifier
  • Clarivate Analytics Document Solution ID: 400RR
  • PubMed Identifier: 19105193
ISSN
0947-6539
Ausgabe der Veröffentlichung
4
Zeitschrift
CHEMISTRY-A EUROPEAN JOURNAL
Schlüsselwörter
  • hydrides
  • inverse crown compounds
  • magnetic properties
  • manganese
  • metalation
  • sodium
Paginierung
856 - 863
Datum der Veröffentlichung
2009
Status
Published
Titel
Structural and Magnetic Insights into the Trinuclear Ferrocenophane and Unexpected Hydrido Inverse Crown Products of Alkali-Metal-Mediated Manganation(II) of Ferrocene
Sub types
  • Article
Ausgabe der Zeitschrift
15

Data source: Web of Science (Lite)

Other metadata sources:
Abstract
<jats:title>Abstract</jats:title><jats:p>With the aim of introducing the diisopropylamide [N<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>]<jats:sup><jats:bold>−</jats:bold></jats:sup> 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 [Na<jats:sub>2</jats:sub>Mn<jats:sub>2</jats:sub> (μ‐H)<jats:sub>2</jats:sub>{N(<jats:italic>i</jats:italic>Pr)<jats:sub>2</jats:sub>}<jats:sub>4</jats:sub>]⋅2 toluene (<jats:bold>1</jats:bold>), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces <jats:bold>1</jats:bold> 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(C<jats:sub>5</jats:sub>H<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>}<jats:sub>3</jats:sub>{Mn<jats:sub>3</jats:sub>Na<jats:sub>2</jats:sub>(N<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub> (HN<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>}] (<jats:bold>2</jats:bold>) in an isolated crystalline yield of 81 %. Both <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> have been characterised by X‐ray crystallographic studies. The magnetic properties of paramagnetic <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> have also been examined by variable‐temperature magnetisation measurements on powdered samples. For <jats:bold>1</jats:bold>, the room‐temperature value for <jats:italic>χT</jats:italic> is 3.45 cm<jats:sup>3</jats:sup> K mol<jats:sup>−1</jats:sup>, and on lowering the temperature a strong antiferromagnetic coupling between the two Mn ions is observed. For <jats:bold>2</jats:bold>, the room‐temperature value for <jats:italic>χT</jats:italic> is 4.06 cm<jats:sup>3</jats:sup> K mol<jats:sup>−1</jats:sup>, which is significantly lower than the expected value for three isolated paramagnetic Mn<jats:sup>II</jats:sup> ions.</jats:p>
Autoren
  • Victoria L Blair
  • Luca M Carrella
  • William Clegg
  • Jan Klett
  • Robert E Mulvey
  • Eva Rentschler
  • Luca Russo
DOI
10.1002/chem.200802086
eISSN
1521-3765
ISSN
0947-6539
Ausgabe der Veröffentlichung
4
Zeitschrift
Chemistry – A European Journal
Sprache
en
Online publication date
2009
Paginierung
856 - 863
Datum der Veröffentlichung
2009
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/chem.200802086
Datum der Datenerfassung
2023
Titel
Structural and Magnetic Insights into the Trinuclear Ferrocenophane and Unexpected Hydrido Inverse Crown Products of Alkali‐Metal‐Mediated Manganation(II) of Ferrocene
Ausgabe der Zeitschrift
15

Data source: Crossref

Abstract
With the aim of introducing the diisopropylamide [NiPr(2)](-) 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 [Na(2)Mn(2) (mu-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(C(5)H(4))(2)}(3){Mn(3)Na(2)(NiPr(2))(2) (HNiPr(2))(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 chiT is 3.45 cm(3) 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 chiT is 4.06 cm(3) K mol(-1), which is significantly lower than the expected value for three isolated paramagnetic Mn(II) ions.
Addresses
  • WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, UK.
Autoren
  • Victoria L Blair
  • Luca M Carrella
  • William Clegg
  • Jan Klett
  • Robert E Mulvey
  • Eva Rentschler
  • Luca Russo
DOI
10.1002/chem.200802086
eISSN
1521-3765
Externe Identifier
  • PubMed Identifier: 19105193
Funding acknowledgements
  • Engineering and Physical Sciences Research Council: EP/D076889/1
  • Engineering and Physical Sciences Research Council: GR/T27228/01
Open access
false
ISSN
0947-6539
Ausgabe der Veröffentlichung
4
Zeitschrift
Chemistry (Weinheim an der Bergstrasse, Germany)
Sprache
eng
Medium
Print
Paginierung
856 - 863
Datum der Veröffentlichung
2009
Status
Published
Datum der Datenerfassung
2008
Titel
Structural and magnetic insights into the trinuclear ferrocenophane and unexpected hydrido inverse crown products of alkali-metal-mediated manganation(II) of ferrocene.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
15

Data source: Europe PubMed Central

Abstract
With the aim of introducing the diisopropylamide [NiPr(2)](-) 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 [Na(2)Mn(2) (mu-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(C(5)H(4))(2)}(3){Mn(3)Na(2)(NiPr(2))(2) (HNiPr(2))(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 chiT is 3.45 cm(3) 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 chiT is 4.06 cm(3) K mol(-1), which is significantly lower than the expected value for three isolated paramagnetic Mn(II) ions.
Autoren
  • Victoria L Blair
  • Luca M Carrella
  • William Clegg
  • Jan Klett
  • Robert E Mulvey
  • Eva Rentschler
  • Luca Russo
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/19105193
DOI
10.1002/chem.200802086
eISSN
1521-3765
Ausgabe der Veröffentlichung
4
Zeitschrift
Chemistry
Sprache
eng
Country
Germany
Paginierung
856 - 863
Datum der Veröffentlichung
2009
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2009
Titel
Structural and magnetic insights into the trinuclear ferrocenophane and unexpected hydrido inverse crown products of alkali-metal-mediated manganation(II) of ferrocene.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
15

Data source: PubMed

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