The Role of Anionic Ligands on Photoreactivity in Mo(VI) Dioxo Complexes of the Form MoO2 X2 (NN).

The photoreactivity of d0 metal dioxo complexes in activating C-H bonds has been recently studied.[1-3] We have previously reported that MoO2 Cl2 (bpy-t Bu) is an effective platform for light initiated C-H activation with unique product selectivity for the overall functionalization.[1] Herein we expand on these studies and report the synthesis and photoreactivity of several new Mo(VI) dioxo complexes with the general formula MoO2 (X)2 (NN); where X=F- , Cl- , Br- , CH3 - , PhO- , t BuO- and NN=2,2'-bipyridine (bpy) or 4,4'-tert-butyl-2,2'bipyridine (bpy-t Bu). Among these compounds, MoO2 Cl2 (bpy-t Bu) and MoO2 Br2 (bpy-t Bu) are able to participate in bimolecular photoreactivity with several substrates containing C-H bonds of various types such as allyls, benzyls, aldehydes (RCHO) and alkanes. MoO2 (CH3 )2 bpy and MoO2 (PhO)2 bpy do not participate in bimolecular photoreactions and instead they undergo photodecompositions. Computational studies indicate that the nature of the HOMO and LUMO is critical in supporting photoreactivity, with access to an LMCT (bpy→Mo) being necessary for tractable hydrocarbon functionalization.

Light-Initiated C-H Activation via Net Hydrogen Atom Transfer to a Molybdenum(VI) Dioxo.

MoO2Cl2(bpy-tBu) (1) is shown to be a potent one-electron oxidant upon irradiation with 365 nm light in various solvents, while being a weak two-electron oxidant in the dark. Complex 1 is characterized to activate various types of C-H bonds photochemically, including allylic and benzylic positions as well as alkanes and aldehydes. In all of these oxidations, 1 ultimately forms a bimetallic Mo(V)/Mo(V) species with a µ-oxo ligand (2). Depending on the substrate, the major organic product is identified as either an oxygenated or a C-C coupled (homodimerized) compound along with a minor chlorinated species. The product selectivity is proposed to be dependent upon the relative values between the bond dissociation enthalpy (BDE) of a potentially new C-OH bond within the product versus the BDE of a Mo-OH motif within a Mo(V)O(OH) intermediate. Based on this, we can estimate the BDE for Mo-OH to be 83-93 kcal/mol. Mechanistic studies suggest that the C-H activation occurs via a net hydrogen atom transfer (HAT) from 1* occurring either asynchronously or via a stepwise electron-proton transfer (ET-PT) process. Complex 2 is further demonstrated to reform dioxo 1 in the presence of chemical oxidants.

Sensing of Acetaminophen Drug Using Zn-Doped Boron Nitride Nanocones: a DFT Inspection.

During environmental testing, scientists face the problem of developing and designing a new type of sensor electrode with distinguished stability, high activity, and cost-effectiveness to detect acetaminophen (ACE). Density functional theory (DFT) calculations were used to investigate the interaction and electrical response of Zn-doped and pristine boron nitride nanocones (BNNCs) with and to ACE with the disclination angle of 240°. The adsorption energy for ACE in the Zn-doped was - 56.94 kJ.mol-1. This value for BNNCs was approximately - 26.11 kJ.mol-1. Furthermore, after the adsorption of ACE, the value of band gap (Eg) for Zn-doped BNNCs decreased significantly (from 4.01 to 3.10 eV), thereby increasing the electrical conductivity. However, Eg value of the pristine BNNCs decreased marginally after the adsorption of ACE. Compared with the pristine BNNCs, the Zn-doped BNNCs could be considered promising materials for the detection of ACE and could be employed in electronic sensors. In the Zn-doped BNNCs, the molecular and electrostatic interactions and the creation of Zn-O bond played key roles in the adsorption of ACE. The Zn-doped BNNCs had other merits such as slight recovery time which was approximately 7.09 ms for the desorption of ACE at ambient temperature.