Cytochrome P450s and Galactose Oxidases exploit redox active ligands to form reactive high valent intermediates for oxidation reactions. This strategy works well for the late 3d metals where accessing high valent states is rather challenging. Herein, we report the oxidation of Ni II (salenwith mCPBA (meta-chloroperoxybenzoic acid) to form a fleeting Ni III bisphenoxyl diradical species, in CH 3 CN and CH 2 Cl 2 at À 40 °C. Electrochemical and spectroscopic analyses using UV/Vis, EPR, and resonance Raman spectroscopies revealed oxidation events both on the ligand and the metal centre to yield a Ni III bisphenoxyl diradical species. DFT calculations found the electronic structure of the ligand and the dconfiguration of the metal center to be consistent with a Ni III bisphenoxyl diradical species. This three electron oxidized species can perform hydrogen atom abstraction and oxygen atom transfer reactions.
The formal Cu(III) complex [Cu(CF 3 ) 4 ] 1À has often served as a paradigmatic example of challenging oxidation state assignment -with many reports proposing conflicting descriptions.Here we report a computational analysis of this compound, employing Energy Decomposition Analysis and Intrinsic Bond Orbital Analysis. We present a quasi-d 10 perspective of the metal centre, resulting from ambiguities in d-electron counting. The implications for describing reactions which undergo oxidation state changes, such as the formal reductive elimination from the analogous [Cu(CF 3 ) 3 (CH 2 Ph)] 1À complex (Paeth et al. J. Am. Chem. Soc. 2019, 141, 3153), are probed. Electron flow analysis finds that the changes in electronic structure may be understood as a quasi-d 10 to d 10 transition at the metal centre, rendering this process essentially redox neutral. This is reminiscent of a previously studied formal Ni(IV) complex (Steen et al., Angew. Chem. Int. Ed. 2019, 58, 13133-13139), and indicates that our description of electronic structure has implications for the understanding of elementary organometallic reaction steps.
This paper describes an experimental approach to eliminating the loss of reversibility that surface-bound spiropyrans exhibit when switched with light. Although such fatigue can be controlled in other contexts, on surfaces, the photochromic compounds are held in close proximity to each other and relatively few molecules modulate the properties of a device, leading to a loss of functionality after only a few switching cycles. The switching process was characterized by photoelectron spectroscopy and differences in tunneling currents in the spiropyran and merocyanine forms using eutectic Ga−In. Self-assembled monolayers comprising only the photochromic compounds degraded rapidly, while mixed monolayers with hexanethiol showed different behaviors depending on the relative humidity. Under dry conditions, no chemical degradation was observed and the switching process was reversible over at least 100 cycles. Under humid conditions, no degradation occurred, but the switching process became irreversible. The absence of degradation observed in mixed monolayers is ascribed to the lack of solvation, which increases the barrier to a key bond rotation past the available thermal energy. These results highlight important differences in the contexts in which photochromic compounds are utilized and demonstrate that they can be leveraged to extract device-relevant functionality from surface-bound switches by suppressing fatigue and irreversibility.
Nucleophilic formal gold(–i) and gold(i) complexes are investigated via Intrinsic Bond Orbital analysis and Energy Decomposition Analysis, based on density functional theory calculations.
A systematic study of protodeauration, a crucial step often found in gold catalysis, was performed using isolated vinyl gold(I) complexes. By varying substituents on gold complexes, we explore how their properties influence protodeauration. Phenols were employed as the proton source, and their substituents were also varied, providing insight through variation of their acidity. A linear Hammett correlation is identified for the series of substituted vinyl gold(I) complexes, while a nonlinear trend is found for the series of substituted phenols. Computationally, we reproduce our experimental observations and identify significant noncovalent interactions (NCIs) between the proton donor and vinyl gold(I) complexes. This finding is of particular importance for goldcatalyzed reactions as they often employ linear two-coordinate complexes where the site of the reaction is spatially remote from the ligand bound to gold. The NCIs between substrates and intermediates lead to a significant acceleration of the protodeauration step in this work, opening the door to alternative strategies in the field of gold catalysis.
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