Diruthenium dithiolato cyanides: basic reactivity studies and a post hoc examination of nature's choice of Fe versus Ru for hydrogenogenesis

Inorganic Chemistry
Aaron K JusticeThomas B Rauchfuss

Abstract

The reaction of Ru2(S2C3H6)(CO)6 (1) with 2 equiv of Et4NCN yielded (Et4N)2[Ru2(S2C3H6)(CN)2(CO)4], (Et4N)2[3], which was shown crystallographically to consist of a face-sharing bioctahedron with the cyanide ligands in the axial positions, trans to the Ru-Ru bond. Competition experiments showed that 1 underwent cyanation >100x more rapidly than the analogous Fe2(S2C3H6)(CO)6. Furthermore, Ru2(S2C3H6)(CO)6 underwent dicyanation faster than [Ru2(S2C3H6)(CN)(CO)5]-, implicating a highly electrophilic intermediate [Ru2(S2C3H6)(mu-CO)(CN)(CO)5]-. Ru2(S2C3H6)(CO)6 (1) is noticeably more basic than the diiron compound, as demonstrated by the generation of [Ru2(S2C3H6)(mu-H)(CO)6]+, [1H]+. In contrast to 1, the complex [1H]+ is unstable in MeCN solution and converts to [Ru2(S2C3H6)(mu-H)(CO)5(MeCN)]+. (Et4N)2[3] was shown to protonate with HOAc (pKa = 22.3, MeCN) and, slowly, with MeOH and H2O. Dicyanide [3]2- is stable toward excess acid, unlike the diiron complex; it slowly forms the coordination polymer [Ru2(S2C3H6)(mu-H)(CN)(CNH)(CO)4]n, which can be deprotonated with Et3N to regenerate [H3]-. Electrochemical experiments demonstrate that [3H]- catalyzes proton reduction at -1.8 V vs Ag/AgCl. In contrast to [3]2-, the CO ligands in ...Continue Reading

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Oct 14, 2004·Journal of the American Chemical Society·Aaron K JusticeScott R Wilson
Aug 4, 2005·Journal of the American Chemical Society·Christine A BoykeLuca De Gioia

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Citations

Jun 2, 2016·Journal of Public Health·Kathleen BurgessUNKNOWN Public Health Agency of Canada/Canadian Institutes of Health Research Influenza Research Network (PCIRN)
Dec 12, 2020·Chemical Society Reviews·Julian T KleinhausUlf-Peter Apfel
Nov 14, 2007·Journal of the American Chemical Society·Anne K JonesP Leslie Dutton
May 15, 2007·Journal of the American Chemical Society·Tianbiao Liu, Marcetta Y Darensbourg
Apr 14, 2018·The Journal of Physical Chemistry. a·Christopher J Stromberg, Edwin J Heilweil
Aug 15, 2006·Inorganic Chemistry·Clarite AzerrafDmitri Gelman

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