New derivatives of ferrocenol and 1,1′-ferrocenediol

Starting from the alcohols ferrocenol (Fe(C5H5)(C5H4-OH), Fc-OH) and 1,1'-ferrocenediol (Fe(C5H4-OH)(2), fc(OH)(2)), a series of new ferrocene derivatives has been prepared, in which oxygen is directly connected with the ferrocene unit. The reactions with organoelement chlorides such as Me3SnCl, (BuPCl2)-Bu-t, (Bu2PCl)-Bu-t and (Bu2AsCl)-Bu-t lead to complexes containing the heteronuclear groups O-Sn, O-P, and O-As, respectively. The analogous trimethylsiloxy derivatives, Fc-OSiMe3 and fc(OSiMe3)(2), are obtained by the reaction of the lithiated ferrocenes, FcLi or fcLi(2), with bis(trimethylsilyl)peroxide, Me3Si-OO-SiMe3. The monofunctional ferrocenol reacts with carboxylic acid chlorides to give di- or trinuclear ferrocenol esters depending on the structure of the acid chloride. The corresponding reactions of the bifunctional 1,1'-ferrocenediol lead to either mononuclear [n]ferrocenophanes, or dinuclear [n.n]ferrocenophanes depending on the nature of the acid chloride. The new compounds were characterized by their H-1- and C-13-NMR spectra as well as their mass spectra. The molecular structures of diferrocenyl phthalate, o-C6H4(CO(2)Fc)(2) and of the [6]ferrocenophane fcO(2)[(CO)(2)oC(6)H(4)] were determined by single crystal X-ray structure analyses. (C) 1998 Elsevier Science S.A. All rights reserved.