The inverse sandwich complex [(K(18-crown-6))2Cp][CpFe(CO)2] - unpredictable redox reactions of [CpFe(CO)2]I with the silanides Na[SiRtBu2] (R = Me, tBu) and the isoelectronic phosphanyl borohydride K[PtBu2BH3]CCDC 832033 ([(K(18-crown-6))2Cp][5]), 832034 ([K(18-crown-6)][5]), 832031 (6). For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2dt00031h

• Main Authors: Sänger, Inge, Kückmann, Theresa I, Dornhaus, Franz, Bolte, Michael, Wagner, Matthias, Lerner, Hans-Wolfram
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt00031h

The dimeric iron carbonyl [CpFe(CO) 2 ] 2 and the iodosilanes t Bu 2 RSiI were obtained from the reaction of [CpFe(CO) 2 ]I with the silanides Na[SiR t Bu 2 ] (R = Me, t Bu) in THF. By the reactions of [CpFe(CO) 2 ]I and Na[SiR t Bu 2 ] (R = Me, t Bu) the disilanes t Bu 2 RSiSiR t Bu 2 (R = Me, t Bu) were additionally formed using more than one equivalent of the silanide. In this context it should be noted that reduction of [CpFe(CO) 2 ] 2 with Na[Si t Bu 3 ] gives the disilanes t Bu 3 SiSi t Bu 3 along with the sodium ferrate [(Na(18-crown-6)) 2 Cp][CpFe(CO) 2 ]. The potassium analogue [(K(18-crown-6)) 2 Cp][CpFe(CO) 2 ] (orthorhombic, space group Pmc 2 1 ), however, could be isolated as a minor product from the reaction of [CpFe(CO) 2 ]I with [K(18-crown-6)][P t Bu 2 BH 3 ]. The reaction of [CpFe(CO) 2 ] 2 with the potassium benzophenone ketyl radical and subsequent treatment with 18-crown-6 yielded the ferrate [K(18-crown-6)][CpFe(CO) 2 ] in THF at room temperature. The crown ether complex [K(18-crown-6)][CpFe(CO) 2 ] was analyzed using X-ray crystallography (orthorhombic, space group Pna 2 1 ) and its thermal behaviour was investigated. The solid-state structure of [(K(18-crown-6)) 2 Cp][CpFe(CO) 2 ] is composed of discrete [CpFe(CO) 2 ] anions and inverse sandwich cations which consist of two [K(18-crown-6)] units and one Cp ring.