Heterobimetallic compounds [Ru(η5-Cp)(dppf)X] (X = Cl, Br, I and N3): synthesis, electrochemical analysis, and the crystal structure of [Ru(η5-Cp)(dppf)I] [dppf = 1,1′-bis(diphenylphosphino)ferrocene]

Abstract

Heterobimetallic compounds [Ru(g 5 -Cp)(dppf)X] (X 5 Cl, Br, I and N 3 ): synthesis, electrochemical analysis, and the crystal structure of [Ru(g 5 -Cp)(dppf)I] [dppf 5 1,1 0 -bis- (3) and [Ru(g 5 -Cp)(dppf)N 3 ] (4) were obtained by reactions of [Ru(g 5 -Cp)(PPh 3 ) 2 Cl] with 1,1 0 -bis(diphenylphosphino) ferrocene (dppf) and characterized by IR, NMR ( 1 H, 13 C and 31 P), 57 Fe Mössbauer spectroscopy and cyclic voltammetry. Additionally, the compound (3) was structurally characterized by X-ray crystallography, and the results were as follows: orthorhombic, Pbca, a = 18.2458 (10), b = 20.9192(11), c = 34.4138(19) Å , a = b = c = 90°, V = 13135.3(12) Å 3 and Z = 16.

Synthesis and Characterization of Cerium and Yttrium Alkoxide Complexes Supported by Ferrocene-Based Chelating Ligands

“…The 31 P NMR spectrum of 3-Ce(O t Bu) 2 displayed a peak at 34.6 ppm, comparable to values reported for analogous complexes. 54 (23)°, respectively, indicating that there is a larger deviation from the planarity of the NCeO phenoxide arrangements in the latter compound. It is likely that this difference is a consequence of the more flexible PdN than CdN linkage found in 2-Ce(O t Bu) 2 .…”

“…While complexes of transition metals have been targeted before to study redox isomerism, 15,18,[20][21][22][23][24] lanthanide and actinide examples are still limited. 19,25 With a strongly oxidizing metal center like cerium(IV), there exists the potential for redox events to occur, effectively changing the ferrocene backbone of the ancillary ligand into ferrocenium upon complexation.…”

“…While complexes of transition metals have been targeted before to study redox isomerism, ,,− lanthanide and actinide examples are still limited. , With a strongly oxidizing metal center like cerium(IV), there exists the potential for redox events to occur, effectively changing the ferrocene backbone of the ancillary ligand into ferrocenium upon complexation. Cerium(IV) is a good candidate for this process since it has a redox potential of 0.88 V in water, while ferrocene has a redox potential of 0.00 V (both measured versus Cp 2 Fe/Cp 2 Fe + ) .…”