Reichl Stephan, Riedlberger Felix, Piesch Martin, Balázs Gábor, Seidl Michael, Scheer Manfred
Institute of Inorganic Chemistry, University Regensburg Universitätsstraße 31 93053 Regensburg Germany
Chem Sci. 2023 May 30;14(26):7285-7290. doi: 10.1039/d3sc01488f. eCollection 2023 Jul 5.
By salt metathesis reactions of the anionic complexes of the type [CpFe(-PR)] (R = Bu (1a), Me (1b), -C[triple bond, length as m-dash]CPh (1c); Cp = 1,2,3,4,5-pentamethylcyclopentadienyl) with organic electrophiles (XR; X = halogen; R = (CH)Br, (CH)Br, Me) a variety of organo-substituted polyphosphorus ligand complexes of the type [CpFe(-PRR)] (2) are obtained. Thereby, organic substituents with different functional groups (FG), such as halogens or nitriles, are introduced. In [CpFe(-PRR')] (2a: R = Bu, R' = (CH)Br), the bromine substituent can be easily substituted, leading to functionalized complexes [{CpFe(-PBu)}(CH){CpFe(-PMe)}] (4) and [CpFe(-PRR')] (5) (R = Bu, R' = (CH)PPh) or by abstraction of a phosphine to the asymmetric substituted phosphine Bu(Bn)P(CH)Bn (6). The reaction of the dianionic species [K(dme)][CpFe(-P)] (I') with bromo-nitriles leads to [CpFe{-P((CH)CN)}] (7), allowing the introduction of two functional groups attached to one phosphorus atom. 7 reacts with ZnBr in a self-assembly reaction to form the supramolecular compound [CpFe{-P((CH)CN)}ZnBr] (8).
通过类型为[CpFe(-PR)]（R = Bu（1a），Me（1b），-C≡CPh（1c）；Cp = 1,2,3,4,5-五甲基环戊二烯基）的阴离子配合物与有机亲电试剂（XR；X = 卤素；R = (CH)Br，(CH)Br，Me）发生复分解反应，可得到多种类型为[CpFe(-PRR)]（2）的有机取代多磷配体配合物。由此引入了具有不同官能团（FG）的有机取代基，如卤素或腈基。在[CpFe(-PRR')]（2a：R = Bu，R' = (CH)Br）中，溴取代基可被轻易取代，生成功能化配合物[{CpFe(-PBu)}(CH){CpFe(-PMe)}]（4）和[CpFe(-PRR')]（5）（R = Bu，R' = (CH)PPh），或者通过脱去一个膦得到不对称取代膦Bu(Bn)P(CH)Bn（6）。双阴离子物种[K(dme)][CpFe(-P)]（I'）与溴代腈反应生成[CpFe{-P((CH)CN)}]（7），从而能够在一个磷原子上引入两个官能团。7与ZnBr通过自组装反应形成超分子化合物[CpFe{-P((CH)CN)}ZnBr]（8）。
