Direct-Acting Pumping Engine

Mathieson, J. W.

doi:10.1038/scientificamerican03111876-164asupp

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“…Compound 5 gives a well-resolved 1 H NMR spectrum (Figure S18), consistent with the solid-state structure and a Ru IV -O-Ru IV formulation. 56 Complex 5 was isolated in 30% yield after a reaction time of 1 h, but this species is gradually consumed in the reaction mixture (with concomitant formation of CO 2 ) such that it is completely absent after 16 h. S19). The formation of CO 2 and minor quantities of the aforementioned oxo cubanes imply the presence of an oxidizing agent that decomposes organic ligands (e.g., acetate).…”

Section: Reactivity Studiesmentioning

confidence: 99%

Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal Ru^V–Oxo with Significant Oxyl Radical Character

et al. 2019

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High-valent Ru V -oxo intermediates have long been proposed in catalytic oxidation chemistry, but investigations into their electronic and chemical properties have been limited due to their reactive nature and rarity. The incorporation of Ru into the [Co 3 O 4 ] subcluster via the singlestep assembly reaction of Co II (OAc) 2 (H 2 O) 4 (OAc = acetate), perruthenate (RuO 4 − ), and pyridine (py) yielded an unprecedented Ru(O)Co 3 (μ 3 -O) 4 (OAc) 4 (py) 3 cubane featuring an isolable, yet reactive, Ru Voxo moiety. EPR, ENDOR, and DFT studies reveal a valence-localized [Ru V (S = 1/2)Co III 3 (S = 0)O 4 ] configuration and non-negligible covalency in the cubane core. Significant oxyl radical character in the Ru V -oxo unit is experimentally demonstrated by radical coupling reactions between the oxo cubane and both 2,4,6-tri-tert-butylphenoxyl and trityl radicals. The oxo cubane oxidizes organic substrates and, notably, reacts with water to form an isolable μ-oxo bis-cubane complex [(py) 3 (OAc) 4 Co 3 (μ 3 -O) 4 Ru]-O-[RuCo 3 (μ 3 -O) 4 (OAc) 4 (py) 3 ]. Redox activity of the Ru Voxo fragment is easily tuned by the electron-donating ability of the distal pyridyl ligand set at the Co sites demonstrating strong electronic communication throughout the entire cubane cluster. Natural bond orbital calculations reveal cooperative orbital interactions of the [Co 3 O 4 ] unit in supporting the Ru V -oxo moiety via a strong π-electron donation.

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Section: Reactivity Studiesmentioning

confidence: 99%

Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal Ru^V–Oxo with Significant Oxyl Radical Character

et al. 2019

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Direct-Acting Pumping Engine

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Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal Ru^V–Oxo with Significant Oxyl Radical Character

Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal Ru^V–Oxo with Significant Oxyl Radical Character

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Direct-Acting Pumping Engine

Cited by 1 publication

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Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal RuV–Oxo with Significant Oxyl Radical Character

Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal RuV–Oxo with Significant Oxyl Radical Character

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Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal Ru^V–Oxo with Significant Oxyl Radical Character

Isolation and Study of Ruthenium–Cobalt Oxo Cubanes Bearing a High-Valent, Terminal Ru^V–Oxo with Significant Oxyl Radical Character