Catalytic C-H Trifluoromethylation of Arenes and Heteroarenes via Visible Light Photoexcitation of a Co(III)-CF Complex.

A cobalt photocatalyst for direct trifluoromethylation of (hetero)arene C(sp)-H bonds is described and shown to operate via visible light activation of a Co-CF intermediate, which functions as a combined chromophore and organometallic reaction center. Chemical oxidations of previously reported (OCO)Co complexes containing a redox-active [OCO] pincer ligand afford a Co-CF complex two oxidation states above Co(II). Computational and spectroscopic studies are consistent with formulation of the product as [(OCO)Co(CF)(THF)(OTf)] () containing an open-shell [OCO] radical ligand bound to a = 0 Co(III) center.

Photoinduced Cobalt(III)-Trifluoromethyl Bond Activation Enables Arene C-H Trifluoromethylation.

Visible-light capture activates a thermodynamically inert Co -CF bond for direct C-H trifluoromethylation of arenes and heteroarenes. New trifluoromethylcobalt(III) complexes supported by a redox-active [OCO] pincer ligand were prepared. Coordinating solvents, such as MeCN, afford green, quasi-octahedral [( OCO)Co (CF )(MeCN) ] (2), but in non-coordinating solvents the complex is red, square pyramidal [( OCO)Co (CF )(MeCN)] (3).

Redox-Active Bis(phenolate) N-Heterocyclic Carbene [OCO] Pincer Ligands Support Cobalt Electron Transfer Series Spanning Four Oxidation States.

A new family of low-coordinate Co complexes supported by three redox-noninnocent tridentate [OCO] pincer-type bis(phenolate) N-heterocyclic carbene (NHC) ligands are described. Combined experimental and computational data suggest that the charge-neutral four-coordinate complexes are best formulated as Co(II) centers bound to closed-shell [OCO] dianions, of the general formula [(OCO)CoL] (where L is a solvent-derived MeCN or THF). Cyclic voltammograms of the [(OCO)CoL] complexes reveal three oxidations accessible at potentials below 1.

Harnessing redox-active ligands for low-barrier radical addition at oxorhenium complexes.

The addition of an [X](+) electrophile to the five-coordinate oxorhenium(V) anion [Re(V)(O)(ap(Ph))(2)](-) {[ap(Ph)](2-) = 2,4-di-tert-butyl-6-(phenylamido)phenolate} gives new products containing Re-X bonds. The Re-X bond-forming reaction is analogous to oxo transfer to [Re(V)(O)(ap(Ph))(2)](-) in that both are 2e(-) redox processes, but the electronic structures of the products are different. Whereas oxo addition to [Re(V)(O)(ap(Ph))(2)](-) yields a closed-shell [Re(VII)(O)(2)(ap(Ph))(2)](-) product of 2e(-) metal oxidation, [Cl](+) addition gives a diradical Re(VI)(O)(ap(Ph))(isq(Ph))Cl product ([isq(Ph)](•-) = 2,4-di-tert-butyl-6-(phenylimino)semiquinonate) with 1e(-) in a Re d orbital and 1e(-) on a redox-active ligand.

Redox-active ligand-mediated oxidative addition and reductive elimination at square planar cobalt(III): multielectron reactions for cross-coupling.

Square planar cobalt(III) complexes with redox-active amidophenolate ligands are strong nucleophiles that react with alkyl halides, including CH(2)Cl(2), under gentle conditions to generate stable square pyramidal alkylcobalt(III) complexes. The net electrophilic addition reactions formally require 2e(-) oxidation of the metal fragment, but there is no change in metal oxidation state because the reaction proceeds with 1e(-) oxidation of each amidophenolate ligand. Although the four-coordinate complexes are very strong nucleophiles, they are mild outer-sphere reductants.

Deoxygenation of nitroxyl radicals by oxorhenium(V) complexes with redox-active ligands.

Five-coordinate oxorhenium(V) anions with redox-active catecholate ligands deoxygenate stable nitroxyl radicals, including TEMPO(*), to afford dioxorhenium(VII) complexes and aminyl radical-derived products. A structural homologue with redox-inert oxalate ligands does not react with TEMPO(*). Redox-active ligands are proposed to lower the kinetic barrier to TEMPO(*) deoxygenation by giving access to 1e(-) redox steps that are crucial for the formation and stabilization of intermediate species.

Redox-active ligands facilitate bimetallic O2 homolysis at five-coordinate oxorhenium(V) centers.

Five-coordinate oxorhenium(V) anions with redox-active catecholate and amidophenolate ligands are shown to effect clean bimetallic cleavage of O(2) to give dioxorhenium(VII) products. A structural homologue with redox-inert oxalate ligands does not react with O(2). Redox-active ligands lower the kinetic barrier to bimetallic O(2) homolysis at five-coordinate oxorhenium(V) by facilitating formation and stabilization of intermediate O(2) adducts.

Reactions of tetrabromocatecholatomanganese(III) complexes with dioxygen.

New five- and six-coordinate complexes containing the [Mn(III)(Br4cat)2](-) core (Br4cat(2-) = tetrabromo-1,2-catecholate) have been prepared. Homoleptic [Mn(III)(Br4cat)3](3-) reacts rapidly with O2 to produce tetrabromo-1,2-benzoquinone (Br4bq). The [Mn(III)(Br4cat)2](-) fragment is a robust catalytic platform for the aerobic conversion of catechols to quinones.

Mechanistic studies of Hangman salophen-mediated activation of O-O bonds.

Stopped-flow kinetic studies of a HSX-Mn-SalophOMe (1) catalyst provide spectroscopic evidence for the direct generation of a manganese(V) oxo salophen from a manganese(III) perbenzoate. The O-O bond heterolysis reaction that produces the oxo is not facilitated by intramolecular proton transfer from the acid hanging group of the HSX platform. Instead, the hanging group stabilizes the catalyst against oxidative degradation and, consistent with recent predictions of theory, is geometrically matched to promote the end-on coordination of a H2O2 substrate prior to its oxidation at the manganese(V) oxo center.

Molecular chemistry of consequence to renewable energy.

Energy conversion cycles are aimed at driving unfavorable, small-molecule activation reactions with a photon harnessed directly by a transition-metal catalyst or indirectly by a transition-metal catalyst at the surface of a photovoltaic cell. The construction of such cycles confronts daunting challenges because they rely on chemical transformations not understood at the most basic levels. These transformations include multielectron transfer, proton-coupled electron transfer, and bond-breaking and -making reactions of energy-poor substrates.

Nucleophilic aromatic substitution on aryl-amido ligands promoted by oxidizing osmium(IV) centers.

Addition of amine nucleophiles to acetonitrile solutions of the OsIV anilido complex TpOs(NHPh)Cl2 (1) [Tp = hydrotris(1-pyrazolyl)borate] gives products with derivatized anilido ligands, i.e., TpOs[NH-p-C6H4(N(CH2)5)]Cl2 (2) from piperidine and TpOs[NH-p-C6H4N(CH2)4]Cl2 (3) from pyrrolidine.

Slow hydrogen atom self-exchange between Os(IV) anilide and Os(III) aniline complexes: relationships with electron and proton transfer self-exchange.

Hydrogen atom, proton and electron transfer self-exchange and cross-reaction rates have been determined for reactions of Os(IV) and Os(III) aniline and anilide complexes. Addition of an H-atom to the Os(IV) anilide TpOs(NHPh)Cl(2) (Os(IV)NHPh) gives the Os(III) aniline complex TpOs(NH(2)Ph)Cl(2) (Os(III)NH(2)Ph) with a new 66 kcal mol(-1) N-H bond. Concerted transfer of H* between Os(IV)NHPh and Os(III)NH(2)Ph is remarkably slow in MeCN-d(3), with k(ex)(H*) = (3 +/- 2) x 10(-3) M(-1) s(-1) at 298 K.

Synthesis and Structure of an Air-Stable, Free-Radical Cobalt(III) Semiquinone Complex.

The air-stable, free-radical, low-spin Co(III) complex, (Bu(4)N)(2) [3,5-Co(DBSQ)(CN)(4)].(1)/(2)H(2)O.(1)/(4)CH(2)Cl(2) (1), where 3,5-DBSQ is the semiquinone anion derived from the one-electron reduction of 3,5-di-tert-butyl-1,2-benzoquinone, has been synthesized by the reaction of the cobalt(II) tetramer [Co(3,5-DBSQ)(2)](4) with Bu(4)NCN in THF.