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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
Author(s) -
Blair Victoria L.,
Carrella Luca M.,
Clegg William,
Klett Jan,
Mulvey Robert E.,
Rentschler Eva,
Russo Luca
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200802086
Subject(s) - ferrocene , chemistry , toluene , alkali metal , crystallography , bimetallic strip , paramagnetism , metal , yield (engineering) , metal ions in aqueous solution , inorganic chemistry , organic chemistry , materials science , physics , electrode , quantum mechanics , metallurgy , electrochemistry
Abstract With the aim of introducing the diisopropylamide [N i Pr 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 (μ‐H) 2 {N( i Pr) 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 (N i Pr 2 ) 2 (HN i Pr 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 χT 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 χT is 4.06 cm 3 K mol −1 , which is significantly lower than the expected value for three isolated paramagnetic Mn II ions.