Structural and Magnetic Insights into the Trinuclear Ferrocenophane and Unexpected Hydrido Inverse Crown Products of Alkali‐Metal‐Mediated Manganation(II) of Ferrocene |
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Authors: | Victoria L. Blair Luca M. Carrella William Clegg Prof. Jan Klett Dr. Robert E. Mulvey Prof. Dr. Eva Rentschler Prof. Dr. Luca Russo Dr. |
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Affiliation: | 1. WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK), Fax: (+44)?141‐552‐0876;2. Institut für Anorganische Chemie und Analytische Chemie, Johannes‐Gutenberg‐Universit?t Mainz, Duesbergweg 10–14, 55128 Mainz (Germany);3. School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU (UK) |
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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 (μ‐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 χT 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 χT is 4.06 cm3 K mol?1, which is significantly lower than the expected value for three isolated paramagnetic MnII ions. |
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Keywords: | hydrides inverse crown compounds magnetic properties manganese metalation sodium |
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