Sequential Oxygenation of Bis(ß-diketiminate) on a Selective Diruthenium Platform.

ABSTRACT

This article demonstrated the redox-noninnocent phenylene-linked bis(ß-diketiminate) (L2-)-bridged first example of isomeric diruthenium(III)-acac species (acac = acetylacetonate) and its ability to activate dioxygen. The coordination of deprotonated L2- to the {Ru(acac)2} in bis(bidentate) mode led to isomeric {(acac)2RuIII}2(µ-L2-) (S = 1, 1-trans/1-cis, green). 1 displayed Ru(III)-based anisotropic EPR in CH3CN but without the resolution of the forbidden (ΔMs = 2) g1/2 signal at 77 K. 1-cis, however, slowly transformed to the energetically favored 1-trans form. 1 underwent two-step oxygenation at the Cß sites of L2- to form the ß-diketiminate/α-ketodiimine (L'-)-bridged mixed valent (acac)2RuIII(µ-L'-)RuII(acac)2 (2, S = 1/2, pink) followed by bis(α-ketodiimine) (L″)-bridged isovalent (acac)2RuII(µ-L″)RuII(acac)2 (3, S = 0, red). The role of O2 toward 1 → 2/3 was corroborated by 18O2 labeling experiment. Redox steps of 1-3 varied as a function of isomeric identity, bridge, and metal oxidation state. The calculated MOs and Mulliken spin densities attributed to the noninnocence of L2-, L'-, and L″ in the respective complexes. Spectrophotometric monitoring of 1 → 2 revealed pseudo-first-order rate constants (105k s-1) of 1.8 (303 K), 3.5 (313 K), 7.7 (323 K), and 17.0 (333 K) and ΔH⧧/ΔS⧧/ΔG⧧ of 14.3 kcal mol-1/-33.1 cal mol-1 K-1/24.2 kcal mol-1 (298 K), respectively. Moreover, characterization of the short-lived blue intermediate obtained during the conversion of 1 → 2/3 upon exposure to O2 supported its valence tautomeric form (VT1, RuIII-L2--RuIII ↔ RuIII-L•--RuII, S = 1), which in effect facilitated oxygen activation at the ligand backbone.