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1,10-Phenanthroline-5,6-dione (Phd) complexes of group 3 and lanthanide elements having formulae Ln(hfac) 3  (Phd) (Ln = Y, Eu, Yb; hfac = hexafluoroacetylacetonate) were synthesised and characterised. Complexes of  d -block elements of the type [MCl(Phd)( p -cymene)] +  (M = Ru, Os) were also prepared. In all these species, coordination of the polydentate ligand occurs by the  N -donor moieties, as indicated by DFT calculations. The novel compounds were tested, together with  fac -ReBr(Phd)(CO) 3 , as precursors for the preparation of heterobimetallic  d / f  derivatives. The reaction of the rhenium complex with yttrium or lanthanide anhydrous triflate salts led to the formation of the complexes ReBr(CO) 3  ( N , N′ -Phd- O , O′ )Ln(OTf) 3 (THF) (Ln = Y, Eu, Yb), where the trivalent ions interacted with the quinonoid moiety. The redox properties of the rhenium centre were strongly affected by the coordination of Ln(OTf) 3 , as observed by comparing the cyclic voltammetry measurements carried out on  fac -ReBr(Phd)(CO) 3  and on ReBr(CO) 3  ( N , N′ -Phd- O , O′ )Y(OTf) 3 .

Mononuclear and heterodinuclear phenanthrolinedione complexes of d - and f -block elements ‡