Products Cited in Publications Worldwide Synthesis, Characterization, and Electrooxidation Behavior of Ruthenium Nitrosyl Alkyl/Aryl-Oxides and Thiolates with Equatorial Dicarboxamide Chelates

Synthesis, Characterization, and Electrooxidation Behavior of Ruthenium Nitrosyl Alkyl/Aryl-Oxides and Thiolates with Equatorial Dicarboxamide Chelates

Richter-Addo, George B; Kapfunde, Tsitsi Adelaide; Londono-Salazar, Jennifer; Navamoney, Arulsamy; Yamamoto, Nobuyuki; Shaw, Michael J

DOI:

Abstract

Ten new ruthenium compounds based on the N,N,N,N-chelate Me2bpbMe2 (bpb = 1,2-bis(pyridine-2-carboximido)benzene) have prepared and characterized by 1H NMR and IR spectroscopy. The monocarbonyl compound (Me2bpbMe2)Ru(CO)(H2O) compound was generated from the reaction of the free base Me2bpbMe2H2 with Ru3(CO)12 in refluxing DMF. Isoamyl nitrite reacts with this compound to yield the trans-addition nitrosyl alkoxide (Me2bpbMe2)Ru(NO)(O-i-C5H11). Nitrosothiols similarly add in a formal trans-addition manner to yield (Me2bpbMe2)Ru(NO)(SR/Ar) (SR/Ar = S-i-C5H11, SPh, SC6F4H, SC(Me)2CHNHC(O)Me) derivatives. The (Me2bpbMe2)Ru(NO)(O-i-C5H11) compound undergoes alkoxide exchange reactions with PhOH and HOC6F4H to generate (Me2bpbMe2)Ru(NO)(OPh) and (Me2bpbMe2)Ru(NO)(OC6F4H), respectively. The neutral alkoxide/aryloxide nitrosyl compounds exhibit higher νNO bands (1809-1842 cm-1) relative to their thiolate analogues (1755-1823 cm-1). The X-ray crystal structures of (Me2bpbMe2)Ru(NO)(OPh), (Me2bpbMe2)Ru(NO)(OC6F4H), and (Me2bpbMe2)Ru(NO)(SPh), have been determined, and reveal linear axial (O)N–Ru–O/S linkages consistent with trans positioning of the NO and aryloxide and -thiolate groups, and near-linear Ru–N–O moieties (164–174°) consistent with these complexes being formulated as {RuNO}6 species. The electrooxidation behavior of (Me2bpbMe2)Ru(NO)(OC6F4H), (Me2bpbMe2)Ru(NO)(SC6F4H), and (Me2bpbMe2)Ru(NO)(SPh) were examined by cyclic voltammetry and IR spectroelectrochemistry in CH2Cl2. (Me2bpbMe2)Ru(NO)(OC6F4H) and (Me2bpbMe2)Ru(NO)(SC6F4H) display reversible first oxidations, whereas (Me2bpbMe2)Ru(NO)(SPh) displays an irreversible first oxidation with likely loss of the thiolate ligand. Chemical reactivity of (Me2bpbMe2)Ru(NO)(SPh) with H+ and Me+ results in the generation of the free thiol PhSH and thioether PhSMe, respectively.

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