LAUSR

Abstract The syntheses of the new triple-decker complexes [(triphos)Co(μ,η 3:3 -P 3 )Ru(triphos)](BPh 4 ) 2 ; ( CoP 3 Ru )(BPh 4 ) 2 , [(triphos)Co(μ,η 3:3 -P 3 )Os(triphos)](BPh 4 ) 2 ; ( CoP 3 Os )(BPh 4 ) 2 and [(triphos)Ru(μ,η 3:3 -P 3 )Ru(triphos)]PF 6 ·(CH 3 ) 2 CO; ( RuP 3 Ru )PF 6 ·(CH 3 ) 2 CO, three new members of the [(tripod)M(μ-P 3 )M′(tripod)] n+ ( MP3M ′ n+ ) family are described. The structure of the homodinuclear complex ( RuP 3 Ru )PF 6 ·(CH 3 ) 2 CO is also reported. This latter compound has a structure similar to that of the other members of the series and shows an M⋯M separation among the longest hitherto found in these compounds. An electrochemical study shows that they are stable in various oxidation states with a VEN value ranging between 28 and 34. A reasoning around the redox data shows a progressive shift of two pairs of redox processes, corresponding to the VEN variation 30/31-31/32 and 32/33-33/34, which almost rigidly moves in the cathode direction as the overall charge of the homoelectronic compound decreases.