Slipped μ-indenyl triple-decker complexes containing (C 4Me4)Co and (C5R5)Ru fragments

Slipped triple-decker complexes with a bridging indenyl ligand, namely [Cb*Co(μ:η5:η6-C9H 7)CoCb*]+ (2, Cb* = C4Me 4) and [Cb*Co(μ:η6-C9H 7)Ru(C5R5)]+ (R = H, 5a; Me, 5b), have been synthesised by electrophilic stacking of [Cb* Co(η5-C9H7)] (1) with [Cb*Co(MeCN)3]+ or [(C5R 5)Ru-(MeCN)3]+ (R = H, Me), respectively. A similar reaction of [(C5R5)Ru(η5-C 9H7)] (R = H, 3a; Me, 3b) with [Cb*Co-(MeCN) 3]+ affords the cations [(C5R 5)Ru(μ:η5:η6-C9H 7)-CoCb*]+ (R = H, 4a; Me, 4b), which are isomeric with 5a,b. Stacking of [Ru(η5-C9H7)2] (7) with [Cb*Co(MeCN)3]+ or [Cb*CoI] x/TlBF4 gives the triple-decker complex [(η5-C9H7)-Ru(μ:η5: η6-C9H7)CoCb*]+ (8). Further reaction of 8 with [Cp*RuCl]4/TlBF4 unexpectedly affords the slipped tetradecker ruthenium complex (Cp*Ru(μ:η5:η6-C9H 7)Ru(μ:η5:η6-C9H 7)RuCp*]2+ (11). The structures of [4b][Co(η-7,8-C2B9H11)2] and [Cp*Ru(η6-C9H7)] (6) have been determined by X-ray diffraction, and the electrochemical behaviour of the complexes prepared has been studied. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.