Generation, Characterization and Reactivity of a High-Valent Mononuclear Cobalt(IV)-Diazide Complex.

High-valent Fe(IV)=O intermediates of metalloenzymes have inspired numerous efforts to generate synthetic analogs to mimic and understand their substrate oxidation reactivities. However, high-valent M(IV) complexes of late transition metals are rare. We have recently reported a novel Co(IV)-dinitrate complex (1-NO3) that activates sp3 C-H bonds up to 87 kcal/mol. In this work, we have shown that the nitrate ligands in 1-NO3 can be replaced by azide, a more basic coordinating base, resulting in the formation of a more potent Co(IV)-diazide species (1-N3) that reacts with substrates (hydrocarbons and phenols) at faster rate constants and activates stronger C-H bonds than the parent complex 1-NO3. We have characterized 1-N3 employing a combination of spectroscopic and computational approaches. Our results clearly show that the coordination of azide leads to the modulation of the Co(IV) electronic structure and the Co(IV/III) redox potential. Together with the higher basicity of azide, these thermodynamic parameters contribute to the higher driving forces of 1-N3 than 1-NO3 for C-H bond activation. Our discoveries are thus insightful for designing more reactive bio-inspired high-valent late transition metal complexes for activating inert aliphatic hydrocarbons.

C-H Bond Activation by a Mononuclear Nickel(IV)-Nitrate Complex.

The recent focus on developing high-valent non-oxo-metal complexes for late transition metals has proven to be an effective strategy to study the rich chemistry of these high-valent species while bypassing the synthetic challenges of obtaining the oxo-metal counterparts. In our continuing work of exploring late transition metal complexes of unusually high oxidation states, we have obtained in the present study a formal mononuclear Ni(IV)-nitrate complex (2) upon 1-e- oxidation of its Ni(III) derivatives (1-OH and 1-NO3). Characterization of these Ni complexes by combined spectroscopic and computational approaches enables deep understanding of their geometric and electronic structures, bonding interactions, and spectroscopic properties, showing that all of them are square planar complexes and exhibit strong π-covalency with the amido N-donors of the N3 ligand. Furthermore, results obtained from X-ray absorption spectroscopy and density functional theory calculations provide strong support for the assignment of the Ni(IV) oxidation state of complex 2, albeit with strong ligand-to-metal charge donation. Notably, 2 is able to oxidize hydrocarbons with C-H bond strength in the range of 76-92 kcal/mol, representing a rare example of high-valent late transition metal complexes capable of activating strong sp3 C-H bonds.

Crystal Structure and C-H Bond-Cleaving Reactivity of a Mononuclear CoIV-Dinitrate Complex.

High-valent FeIV═O intermediates with a terminal metal-oxo moiety are key oxidants in many enzymatic and synthetic C-H bond oxidation reactions. While generating stable metal-oxo species for late transition metals remains synthetically challenging, notably, a number of high-valent non-oxo-metal species of late transition metals have been recently described as strong oxidants that activate C-H bonds. In this work, we obtained an unprecedented mononuclear CoIV-dinitrate complex (2) upon one-electron oxidation of its Co(III) precursor supported by a tridentate dianionic N3 ligand. 2 was structurally characterized by X-ray crystallography, showing a square pyramidal geometry with two coordinated nitrate anions. Furthermore, characterization of 2 using combined spectroscopic and computational methods revealed that 2 is a low-spin (S = 1/2) Co(IV) species with the unpaired electron located on the cobalt dz2 orbital, which is well positioned for substrate oxidations. Indeed, while having a high thermal stability, 2 is able to cleave sp3 C-H bonds up to 87 kcal/mol to afford rate constants and kinetic isotope effects (KIEs) of 2-6 that are comparable to other high-valent metal oxidants. The ability to oxidize strong C-H bonds has yet to be observed for CoIV-O and CoIII═O species previously reported. Therefore, 2 represents the first high-valent Co(IV) species that is both structurally characterized by X-ray crystallography and capable of activating strong C-H bonds.

Hemilabile Proton Relays and Redox Activity Lead to {FeNO} x and Significant Rate Enhancements in NO2- Reduction.

Incorporation of the triad of redox activity, hemilability, and proton responsivity into a single ligand scaffold is reported. Due to this triad, the complexes Fe(PyrrPDI)(CO)2 (3) and Fe(MorPDI)(CO)2 (4) display 40-fold enhancements in the initial rate of NO2- reduction, with respect to Fe(MeOPDI)(CO)2 (7). Utilizing the proper sterics and p Ka of the pendant base(s) to introduce hemilability into our ligand scaffolds, we report unusual {FeNO} x mononitrosyl iron complexes (MNICs) as intermediates in the NO2- reduction reaction. The {FeNO} x species behave spectroscopically and computationally similar to {FeNO}7, an unusual intermediate-spin Fe(III) coupled to triplet NO- and a singly reduced PDI ligand. These {FeNO} x MNICs facilitate enhancements in the initial rate.

Nitrite reduction by a pyridinediimine complex with a proton-responsive secondary coordination sphere.

The proton-responsive pyridinediimine ligand, (DEA)PDI (where (DEA)PDI = [(2,6-(i)PrC6H3)(N[double bond, length as m-dash]CMe)(N(Et)2C2H4)(N[double bond, length as m-dash]CMe)C5H3N]) was utilized for the reduction of NO2(-) to NO. Nitrite reduction is facilitated by the protonated secondary coordination sphere coupled with the ligand-based redox-active sites of [Fe(H(DEA)PDI)(CO)2](+) and results in the formation of the {Fe(NO)2}(9) DNIC, [Fe((DEA)PDI)(NO)2](+).