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 [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.
authors.affiliation: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, UK.
authors.forename: Victoria L
authors.initials: VL
authors.lastname: Blair
authors.forename: Luca M
authors.initials: LM
authors.lastname: Carrella
authors.forename: William
authors.initials: W
authors.lastname: Clegg
authors.forename: Jan
authors.initials: J
authors.lastname: Klett
authors.forename: Robert E
authors.initials: RE
authors.lastname: Mulvey
authors.forename: Eva
authors.initials: E
authors.lastname: Rentschler
authors.forename: Luca
authors.initials: L
authors.lastname: Russo