ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

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

Marco Bortoluzzi, Dario Battistel, Gabriele Albertin, Salvatore Daniele, Francesco Enrichi, and Riccardo Rumonato

Dipartimento di Scienze Molecolari e Nanosistemi, Informatica e Statistica, Università Ca’ Foscari Venezia, Dorsoduro 2137, 30123 Venezia, Italy

E-mail: markos@unive.it

Abstract: 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.

Keywords: 1,10-phenanthroline-5,6-dione – d-block elements – lanthanides – heterobimetallic complexes – cyclic voltammetry

Full paper is available at www.springerlink.com.

DOI: 10.1515/chempap-2015-0140

Chemical Papers 70 (1) 43–52 (2016)