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Outer-Sphere 2?e- /2?H+ Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes.

ABSTRACT: A diverse set of 2?e- /2?H+ reactions are described that interconvert [RuII (bpy)(en*)2 ]2+ and [RuIV (bpy)(en-H*)2 ]2+ (bpy=2,2'-bipyridine, en*=H2 NCMe2 CMe2 NH2 , en*-H=H2 NCMe2 CMe2 NH- ), forming or cleaving different O-H, N-H, S-H, and C-H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3-cyclohexadiene. These proton-coupled electron transfer reactions occur without substrate binding to the ruthenium center, but instead with precursor complex formation by hydrogen bonding. The free energies of the reactions vary over more than 90?kcal?mol-1 , but the rates are more dependent on the type of X-H bond involved than the associated ?G°. There is a kinetic preference for substrates that have the transferring hydrogen atoms in close proximity, such as ortho-tetrachlorobenzoquinone over its para-isomer and 1,3-cyclohexadiene over its 1,4-isomer, perhaps hinting at the potential for concerted 2?e- /2?H+ transfers.

SUBMITTER: Cattaneo M

PROVIDER: S-EPMC5812014 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature

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Outer-Sphere 2 e- /2 H+ Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes.

Cattaneo Mauricio M Ryken Scott A SA Mayer James M JM

Angewandte Chemie (International ed. in English) 20170216 13

A diverse set of 2 e- /2 H+ reactions are described that interconvert [RuII (bpy)(en*)2 ]2+ and [RuIV (bpy)(en-H*)2 ]2+ (bpy=2,2'-bipyridine, en*=H2 NCMe2 CMe2 NH2 , en*-H=H2 NCMe2 CMe2 NH- ), forming or cleaving different O-H, N-H, S-H, and C-H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3-cyclohexadi ...[more]

PMID: 28206699

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Project description:We report the synthesis and characterisation of mixed-metal binuclear ruthenium(II)-vanadium(IV) complexes, which were used as potential photodynamic therapeutic agents for melanoma cell growth inhibition. The novel complexes, [Ru(pbt)2(phen2DTT)](PF6)2·1.5H2O 1 (where phen2DTT = 1,4-bis(1,10-phenanthrolin-5-ylsulfanyl)butane-2,3-diol and pbt = 2-(2'-pyridyl)benzothiazole) and [Ru(pbt)2(tpphz)](PF6)2·3H2O 2 (where tpphz = tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine) were synthesised and characterised. Compound 1 was reacted with [VO(sal-L-tryp)(H2O)] (where sal-L-tryp = N-salicylidene-L-tryptophanate) to produce [Ru(pbt)2(phen2DTT)VO(sal-L-tryp)](PF6)2·5H2O 4; while [VO(sal-L-tryp)(H2O)] was reacted with compound 2 to produce [Ru(pbt)2(tpphz)VO(sal-L-tryp)](PF6)2·6H2O 3. All complexes were characterised by elemental analysis, HRMS, ESI MS, UV-visible absorption, ESR spectroscopy, and cyclic voltammetry, where appropriate. In vitro cell toxicity studies (with the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric assay) via dark and light reaction conditions were carried out with sodium diaqua-4,4',4'',4''' tetrasulfophthalocyaninecobaltate(II) (Na4[Co(tspc)(H2O)2]), [VO(sal-L-tryp)(phen)]·H2O, and the chloride salts of complexes 3 and 4. Such studies involved A431, human epidermoid carcinoma cells; human amelanotic malignant melanoma cells; and HFF, non-cancerous human skin fibroblast cells. Both chloride salts of complexes 3 and 4 were found to be more toxic to melanoma cells than to non-cancerous fibroblast cells, and preferentially led to apoptosis of the melanoma cells over non-cancerous skin cells. The anti-cancer property of the chloride salts of complexes 3 and 4 was further enhanced when treated cells were exposed to light, while no such effect was observed on non-cancerous skin fibroblast cells. ESR and (51)V NMR spectroscopic studies were also used to assess the stability of the chloride salts of complexes 3 and 4 in aqueous media at pH 7.19. This research illustrates the potential for using mixed-metal binuclear ruthenium(II)-vanadium(IV) complexes to fight skin cancer.

Dataset Information

Outer-Sphere 2?e- /2?H+ Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes.

Publications

Outer-Sphere 2 e<sup>-</sup> /2 H<sup>+</sup> Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes.

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