Slipped μ‐Indenyl Triple‐Decker Complexes Containing (C 4 Me 4 )Co and (C 5 R 5 )Ru Fragments

Slipped triple‐decker complexes with a bridging indenyl ligand, namely [Cb*Co(μ:η 5 :η 6 ‐C 9 H 7 )CoCb*] + ( 2 , Cb* = C 4 Me 4 ) and [Cb*Co(μ:η 5 :η 6 ‐C 9 H 7 )Ru(C 5 R 5 )] + (R = H, 5a ; Me, 5b ), have been synthesised by electrophilic stacking of [Cb*Co(η 5 ‐C 9 H 7 )] ( 1 ) with [Cb*Co(MeCN) 3 ] + or [(C 5 R 5 )Ru(MeCN) 3 ] + (R = H, Me), respectively. A similar reaction of [(C 5 R 5 )Ru(η 5 ‐C 9 H 7 )] (R = H, 3a ; Me, 3b ) with [Cb*Co(MeCN) 3 ] + affords the cations [(C 5 R 5 )Ru(μ:η 5 :η 6 ‐C 9 H 7 )CoCb*] + (R = H, 4a ; Me, 4b ), which are isomeric with 5a , b . Stacking of [Ru(η 5 ‐C 9 H 7 ) 2 ] ( 7 ) with [Cb*Co(MeCN) 3 ] + or [Cb*CoI] x /TlBF 4 gives the triple‐decker complex [(η 5 ‐C 9 H 7 )Ru(μ:η 5 :η 6 ‐C 9 H 7 )CoCb*] + ( 8 ). Further reaction of 8 with [Cp*RuCl] 4 /TlBF 4 unexpectedly affords the slipped tetra‐decker ruthenium complex [Cp*Ru(μ:η 5 :η 6 ‐C 9 H 7 )Ru(μ:η 5 :η 6 ‐C 9 H 7 )RuCp*] 2+ ( 11 ). The structures of [ 4b ][Co(η‐7,8‐C 2 B 9 H 11 ) 2 ] and [Cp*Ru(η 6 ‐C 9 H 7 )] ( 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, 69451 Weinheim, Germany, 2006)