Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants

We report a discovery that perfunctionalized icosahedral dodecaborate clusters of the type B_(12)(OCH_2Ar)_(12) (Ar = Ph or C_6F_5) can undergo photo-excitation with visible light, leading to a new class of metal-free photooxidants. Excitation in these species occurs as a result of the charge transfer between low-lying orbitals located on the benzyl substituents and an unoccupied orbital delocalized throughout the boron cluster core. Here we show how these species, photo-excited with a benchtop blue LED source, can exhibit excited-state reduction potentials as high as 3 V and can participate in electron-transfer processes with a broad range of styrene monomers, initiating their polymerization. Initiation is observed in cases of both electron-rich and electron-deficient styrene monomers at cluster loadings as low as 0.005 mol%. Furthermore, photo-excitation of B_(12)(OCH_2C_6F_5)_(12) in the presence of a less activated olefin such as isobutylene results in the production of highly branched poly(isobutylene). This work introduces a new class of air-stable, metal-free photo-redox reagents capable of mediating chemical transformations

Photooxidative Generation of Dodecaborate-Based Weakly Coordinating Anions

Redox-active proanions of the type B_(12)(OCH_2Ar)_(12) [Ar = C_6F_5 (1), 4-CF_3C_6H_4 (2), 3,5-(CF_3)_2C_6H_3 (3)] are introduced in the context of an experimental and computational study of the visible-light-initiated polymerization of a family of styrenes. Neutral, air-stable proanions 1–3 were found to initiate styrene polymerization through single-electron oxidation under blue-light irradiation, resulting in polymers with number-average molecular weights (M_n) ranging from ∼6 to 100 kDa. Shorter polymer products were observed in the majority of experiments, except in the case of monomers containing 4-X (X = F, Cl, Br) substituents on the styrene monomer when polymerized in the presence of 1 in CH_2Cl_2. Only under these specific conditions are longer polymers (>100 kDa) observed, strongly supporting the formulation that reaction conditions significantly modulate the degree of ion pairing between the dodecaborate anion and cationic chain end. This also suggests that 1–3 behave as weakly coordinating anions (WCA) upon one-electron reduction because no incorporation of the cluster-based photoinitiators is observed in the polymeric products analyzed. Overall, this work is a conceptual realization of a single reagent that can serve as a strong photooxidant, subsequently forming a WCA

Perfunctionalized Dodecaborate Clusters as Stable Metal-Free Active Materials for Charge Storage

We report a class of perfunctionalized dodecaborate clusters that exhibit high stability towards high concentration electrochemical cycling. These boron clusters afford several degrees of freedom in material design to tailor properties including solubility and redox potential. The exceptional stability of these clusters was demonstrated using a symmetric flow cell setup for electrochemical cycling between two oxidation states for 45 days, with post-run analysis showing negligible decomposition of the active species (<0.1%). To further probe the limits of this system, a prototype redox flow battery with two different cluster materials was used to determine mutual compatibility. This work effectively illustrates the potential of bespoke boron clusters as robust material platform for electrochemical energy conversion and storage

Tuning the Electrochemical Potential of Perfunctionalized Dodecaborate Clusters Through Vertex Differentiation

We report a new class of redox-­‐active vertex-­‐differentiated dodecaborate clusters featuring pentafluoroaryl groups. These [B12(OR)11NO2] clusters share several unique photophysical properties with their [B12(OR)12] analogues, while exhibiting significantly higher (+0.5 V) redox potentials. This work describes the synthesis, characterization, and isolation of [B12(O-­‐CH2C6F5)11NO2] clusters in all 3 oxidation states (dianion, radical, and neutral). Reactivity to post-­‐functionalization with thiol species via SNAr on the pentafluoroaryl groups is also demonstated

Perfunctionalized Dodecaborate Clusters as Stable Metal-Free Active Materials for Charge Storage

© 2019 American Chemical Society. We report a class of perfunctionalized dodecaborate clusters that exhibit stability during galvanostatic cycling. These boron clusters afford several degrees of freedom in material design to tailor properties including solubility and redox potential. The exceptional stability of these clusters was demonstrated by using a symmetric flow cell setup for electrochemical cycling between two oxidation states for 45 days, with post-run analysis showing negligible decomposition of the active species (<1%). To further probe the limits of this system, a prototype redox flow battery with two different cluster materials was used to determine mutual compatibility. This work effectively illustrates the potential of bespoke boron clusters as robust material platform for electrochemical energy conversion and storage

Tuning the electrochemical potential of perfunctionalized dodecaborate clusters through vertex differentiation

We report a new class of redox-active vertex-differentiated dodecaborate clusters featuring pentafluoroaryl groups. These [B12(OR)11NO2] clusters share several unique photophysical properties with their [B12(OR)12] analogues, while exhibiting significantly higher (+0.5 V) redox potentials. This work describes the synthesis, characterization, and isolation of [B12(O-CH2C6F5)11NO2] clusters in all 3 oxidation states (dianion, radical, and neutral). Reactivity to post-functionalization with thiol species via SNAr on the pentafluoroaryl groups is also demonstrated

Buchwald-Hartwig Amination Using Pd(I) Dimer Precatalysts Supported by Biaryl Phosphine Ligands

We report the synthesis of air-stable Pd(I) dimer complexes featuring biaryl phosphine ligands. Catalytic experiments suggest that these complexes are comptent precatalysts that can mediate cross-coupling amination reactions between aryl halide electrophiles with both aliphatic and aromatic amine nucleophiles. This work represents an expansion of the air-stable precatalyst toolbox for Pd-catalyzed cross-coupling transformations

Photooxidative Generation of Dodecaborate-Based Weakly Coordinating Anions.

Redox-active proanions of the type B12(OCH2Ar)12 [Ar = C6F5 (1), 4-CF3C6H4 (2), 3,5-(CF3)2C6H3 (3)] are introduced in the context of an experimental and computational study of the visible-light-initiated polymerization of a family of styrenes. Neutral, air-stable proanions 1-3 were found to initiate styrene polymerization through single-electron oxidation under blue-light irradiation, resulting in polymers with number-average molecular weights (Mn) ranging from ∼6 to 100 kDa. Shorter polymer products were observed in the majority of experiments, except in the case of monomers containing 4-X (X = F, Cl, Br) substituents on the styrene monomer when polymerized in the presence of 1 in CH2Cl2. Only under these specific conditions are longer polymers (&gt;100 kDa) observed, strongly supporting the formulation that reaction conditions significantly modulate the degree of ion pairing between the dodecaborate anion and cationic chain end. This also suggests that 1-3 behave as weakly coordinating anions (WCA) upon one-electron reduction because no incorporation of the cluster-based photoinitiators is observed in the polymeric products analyzed. Overall, this work is a conceptual realization of a single reagent that can serve as a strong photooxidant, subsequently forming a WCA