Preparation of chalcogenolato-bridged dinuclear Tp*Rh–Cp*Ru complexes (Tp*= hydrotris(3,5-dimethylpyrazol-1-yl)borate, Cp*=η5-pentamethylcyclopentadienyl) and binding of dioxygen to their Ru sites

Abstract

Reactions of [Tp*Rh(coe)(MeCN)](1; Tp*= hydrotris(3,5-dimethylpyrazol-1-yl); coe = cyclooctene) with one equiv of diphenyl dichalcogenides PhEEPh (E = Se, Te) afforded the mononuclear Rh(III) complexes [Tp*Rh(EPh)(2)(MeCN)](2b: E = Se; 2c: E = Te), as reported previously for the formation of [Tp*Rh(SPh)(2)(MeCN)](2a) from the reaction of 1 and PhSSPh. Complexes 2a-2c were treated with the Ru(II) complex [(Cp*Ru)(4)(mu(3)-Cl)(4)](Cp*=eta(5)-C(5)Me(5)) in THF at room temperature, yielding the chalcogenolato-bridged dinuclear complexes [Tp*RhCl(mu-EPh)(2)RuCp*(MeCN)](3). Complex 3a (E = S) in solution was converted slowly into a mixture of 3a and the sterically less encumbered dinuclear complex [Tp*RhCl(SPh)(mu-eta(1)-S-eta(6)-Ph)RuCp*](4a) at room temperature. In 4a, one SPh group binds only to the Rh center as a terminal ligand, while the other SPh group bridges the Rh and Ru atoms by coordinating to the former at the S atom and to the latter with the Ph group in a pi fashion. The Se analogue 3b also underwent a similar transformation under more forcing conditions, e.g. in benzene at reflux, whereas formation of the mu-eta(1)-Te-eta(6)-Ph complex was not observed for the Te analogue 3c even under these forcing conditions. When complexes 3 was dissolved in THF exposed to air, the MeCN ligand bound to Ru was substituted by dioxygen to give the peroxo complexes [Tp*RhCl(mu-EPh)(2)RuCp*(eta(2)-O(2))](5a: E = S; 5b: E = Se; 5c: E = Te). X-Ray analyses have been undertaken to determine the detailed structures for 2c, 3a, 3b, 4a, 5a, 5b, and 5c.

ChemInform Abstract: Temperature and Light Induced Bistability in a Co3[Os(CN)6]2·6H2O Prussian Blue Analogue.

“…This distance corresponded to that reported previously for the two‐electron‐reduction of O 2 into peroxide (O 2 2− )16 and was within the range found for the previously‐reported [Ru(η 2 ‐O 2 )(η 5 ‐C 5 Me 5 )] complexes (1.316(6)–1.416(5) Å) 17–19. This distance was slightly longer than that found in another dinuclear [NiRu] peroxo complex, [Ni(S 2 N 2 )Ru(η 2 ‐O 2 )(η 5 ‐C 5 Me 5 )] + (1.371(8) Å, S 2 N 2 = N , N ′‐bis(2‐mercaptoethyl)‐ N , N ′‐dimethyl‐1,3‐diaminoethane),17 and comparable to that reported in a dinuclear [RhRu] peroxo complex, [Rh(Tp*)(μ‐SPh) 2 Ru(η 2 ‐O 2 )(η 5 ‐C 5 Me 5 )] (1.397(3) Å, Tp*=hydrotris(3,5‐dimethylpyrazol‐1‐yl)) 18…”

Organoselenium ligands in catalysis

“…of diphenyldiselenide PhSeSePh afforded 60 (Scheme 7). [110][111][112][113] Chart 9 Methylselenolate bridged diruthenium complexes.…”

Addition of benzenethiol to terminal alkynes catalyzed by hydrotris(3,5-dimethylpyrazolyl)borate–Rh(III) bis(thiolate) complex: Mechanistic studies with characterization of the key intermediate

“…We have recently reported the first reliable route to synthesize rhodium thiolate complexes with Tp ancillary ligands and their chalcogenolate congeners [20,21]. The Rh(I) complex [TpRh(coe)(MeCN)] (coe = g 2 -cyclooctene) and its hydrotris(3,5-dimethylpyrazolyl)-borate (Tp * ) analog [Tp * Rh(coe)(MeCN)] (1) [22] react with a range of organic disulfides to give mononuclear bis(thiolate) complexes, as exemplified in Eq.…”