Synthetic and oxidation studies of ruthenium(II) phthalocyanine complexes

Abstract

. Can. J. Chem. 58, 1125Chem. 58, (1980. Ruthenium(I1) phthalocyanine complexes of the type RuPcL, (PC = the phthalocyaninato dianion. L = various pyridines, imidazole, dimethylformamide, dimethylsulfoxide, and acetonitrile) may be prepared generally in solution by photolysis of RuPc(C0)L' complexes in the presence of excess L (L' may be the same as L or may be a different ligand), and in some cases a s solids by extraction of crude RuPc with L. The solid RuPc(C0)L monocarbonyls can be formed from reaction of the RuPcL, complexes with carbon monoxide, as well as via an extraction procedure using L with crude RuPc(C0) formed from Ru,(CO),, and phthalocyanine.Chemical or electrochemical oxidation of the RuPcL' or monocarbonyl complexes generates a cationic ruthenium(I1) phthalocyanine radical species and not ruthenium(III), as evidenced by esr and visible spectroscopy. DAVID DOLPHIN, BRIAN R. JAMES, ALAN J. MURRAY et JOHN R. THORNBACK. Can. J. Chem. 58, 1125Chem. 58, (1980. Les complexes phthalocyanine de ruthenium(I1) du type RuPcLz (PC = dianions phthalocyaninato, L = differentes pyridines, imidazole, dimethylformamide, dimethylsulfoxyde et acetonitrile) peuvent generalement i t r e prepares en solution par photolyse des complexes de RuPc(CO)L1 en presence d'un exces de L (L' peut i t r e identique a L ou peut Ctre un ligand different) et dans certains cas ils peuvent i t r e prepares sous forme solide par extraction du RuPc brut avec L . Le solide monocarbonyle RuPc(C0)L peut i t r e forme par la reaction des complexes RuPcL, avec le monoxyde de carbone aussi bien que par le procede d'extraction utilisant L avec le RuPc(C0) brut forme partir de Ru,(CO),, et la phthalocyanine.L'oxydation chimique ou electrochimique de RuPcL, ou des complexes monocarbonyles genere un radical cationique de phthalocyanine de ruthCnium(I1) et non de ruthenium(II1) tel que mis en evidence par la rpe et la spectroscopie visible.[Traduit par le journal]

Synthesis and redox chemistry of octaethylporphyrin complexes of ruthenium(II) and ruthenium(III)

“…5), and are consistent with no accompanying ligand exchange reactions. The reduction potential for this Ru(III)/Ru(II) couple is lower than those of related bis(tertiary phosphine) complexes of Ru(TPP) (9), and is consistent with a relative stabilization of Ru(II1) by the more basic OEP ligand system. Addition of triphenylphosphine to a solution of 7 gave a similar result with formation of what is believed to be the bis- The reaction of cation-radical 8 with triphenylphosphine was very different and involved a reduction to give Ru(0EP)-(CO)(PPh,) (6), probably via the Ru(OEP)(CO) intermediate.…”

“…Cyclic voltammograms were recorded using apparatus previously described (9) with the following modifications: the potential was controlled via an EG and G PARC Model 175 Universal Programmer linked to a Model 173 PAR potentiostat. Scan speed was 250 mV/s unless otherwise indicated.…”

“…Tctra-11-propylammonium trifluoronicthanesulphonatc (13) and tctra-11-butylammonium hexafluorophosphate. TBAH (9,14), wcrc prepared as described in the literature. Tctra-11-butylarnnio~~ium borohydride was kindly provided by B. Tarpey, having been prepared by a method previously described (15).…”

“…CH3CN, THF, and PR,; (porp) = dianion of octaethylporphyrin systems, which are difficult to study directly, is well phyrin (OEP) or meso-tetraphenylporphyrin (TPP) (2,(7)(8)(9). established (1).…”

“…species electrochemically by removal of analogues of these compounds because otherwise reactive inone electron is thought to give a ruthenium(I11) complex as termediates are expected to be more stable for the ruthenium judged by the visible spectrum, and the lack of an esr signal, complexes than for the iron complexes (2,3). This is particuattributable to a cation radical (2,9), while oxidation of the larly relevant in the study of porphyrin cation radicals which carbonyls occurs at the ring to give a T-cation radical species have been suggested as intermediates in a number of natural (7,8). porphyrin systems such as cytochrome P450 (4) and horseIn this study we describe the redox properties of ruthenium radish peroxidase (5).…”