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Global energy consumption is projected to increase, even in the face of substantial declines in energy intensity, at least 2-fold by midcentury relative to the present because of population and economic growth. This demand could be met, in principle, from fossil energy resources, particularly coal. However, the cumulative nature of CO2 emissions in the atmosphere demands that holding atmospheric CO2 levels to even twice their preanthropogenic values by midcentury will require invention, development, and deployment of schemes for carbon-neutral energy production on a scale commensurate with, or larger than, the entire present-day energy supply from all sources combined. Among renewable energy resources, solar energy is by far the largest exploitable resource, providing more energy in 1 hour to the earth than all of the energy consumed by humans in an entire year. In view of the intermittency of insolation, if solar energy is to be a major primary energy source, it must be stored and dispatched on demand to the end user. An especially attractive approach is to store solar-converted energy in the form of chemical bonds, i.e., in a photosynthetic process at a year-round average efficiency significantly higher than current plants or algae, to reduce land-area requirements. Scientific challenges involved with this process include schemes to capture and convert solar energy and then store the energy in the form of chemical bonds, producing oxygen from water and a reduced fuel such as hydrogen, methane, methanol, or other hydrocarbon species.

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Powering the planet: Chemical challenges in solar energy utilization

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The site-selective formation of carbon-carbon bonds through direct functionalizations of otherwise unreactive carbon-hydrogen bonds constitutes an economically attractive strategy for an overall streamlining of sustainable syntheses. In recent decades, intensive research efforts have led to the development of various reaction conditions for challenging C-H bond functionalizations, among which transition-metal-catalyzed transformations arguably constitute thus far the most valuable tool. For instance, the use of inter alia palladium, ruthenium, rhodium, copper, or iron complexes set the stage for chemo-, site-, diastereo-, and/or enantioselective C-H bond functionalizations. Key to success was generally a detailed mechanistic understanding of the elementary C-H bond metalation step, which depending on the nature of the metal fragment can proceed via several distinct reaction pathways. Traditionally, three different modes of action were primarily considered for CH bond metalations, namely, (i) oxidative addition with electronrich late transition metals, (ii) σ-bond metathesis with early transition metals, and (iii) electrophilic activation with electrondeficient late transition metals (Scheme 1). However, more recent mechanistic studies indicated the existence of a continuum of electrophilic, ambiphilic, and nucleophilic interactions. Within this continuum, detailed experimental and computational analysis provided strong evidence for novel C-H bond metalationmechanisms relying on the assistance of a bifunctional ligand bearing an additional Lewis-basic heteroatom, such as that found in (heteroatom-substituted) secondary phosphine oxides or most prominently carboxylates (Scheme 1, iv). This novel insight into the nature of stoichiometric metalations has served as stimulus for the development of novel transformations based on cocatalytic amounts of carboxylates, which significantly broadened the scope of C-H bond functionalizations in recent years, with most remarkable progress being made in palladiumor ruthenium-catalyzed direct arylations and direct alkylations. These carboxylate-assisted C-H bond transformations were mostly proposed to proceed via a mechanism in which metalation takes place via a concerted base-assisted deprotonation. To mechanistically differentiate these intramolecular metalations new acronyms have recently been introduced into the literature, such as CMD (concerted metalationdeprotonation), IES (internal electrophilic substitution), or AMLA (ambiphilic metal ligand activation), which describe related mechanisms and will be used below where appropriate. This review summarizes the development and scope of carboxylates as cocatalysts in transition-metal-catalyzed C-H functionalizations until autumn 2010. Moreover, experimental and computational studies on stoichiometric metalation reactions being of relevance to the mechanism of these catalytic processes are discussed as well. Mechanistically related C-H bond cleavage reactions with ruthenium or iridium complexes bearing monodentate ligands are, however, only covered with respect to their working mode, and transformations with stoichiometric amounts of simple acetate bases are solely included when their mechanism was suggested to proceed by acetate-assisted metalation.

Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope.

Isolation and Structural Characterization of the Terminal Mesityl Azide Complex V(N3Mes)(I)(NRArF)2 and Its Conversion to a Vanadium(V) Imido Complex

Synthesis of zinc sulfide and cadmium sulfide within ROMP block copolymer microdomains

In the presence of NaH, the reaction between N2 and Mo(N[t-Bu]Ar)3 (Ar = 3,5-C6H3Me2) proceeds at room temperature to afford NMo(N[t-Bu]Ar)3 (95%). Lewis acidic silyl triflates (Me3SiOTf + pyridine or (i-Pr)3SiOTf) mediate a reaction between acid chlorides and NMo(N[t-Bu]Ar)3 to yield acyl imidos [RC(O)NMo(N[t-Bu]Ar)3][OTf] (R = Me, 92%; Ph, 75%; t-Bu, 64%). The reduction of [RC(O)NMo(N[t-Bu]Ar)3][OTf] by magnesium anthracene followed by treatment with Me3SiOTf affords molybdenum ketimides, R(Me3SiO)CNMo(N[t-Bu]Ar)3 (R = Me, 82%; Ph, 77%; t-Bu, 46%). Exposing R(Me3SiO)CNMo(N[t-Bu]Ar)3 to SnCl2 or ZnCl2 produces ClMo(N[t-Bu]Ar)3 (71−93% for SnCl2) and RCN (97−99%). Magnesium metal reduces ClMo(N[t-Bu]Ar)3 to Mo(N[t-Bu]Ar)3 (74%), completing a synthetic cycle. New strategies for the functionalization of sterically hindered nitrides and nitrile extrusion from d2 ketimides are presented in the context of a new route for derivatizing N2.

A cycle for organic nitrile synthesis via dinitrogen cleavage.

A multistep synthetic strategy enables the isolation of the niobaziridine−hydride complex Nb(H)(η2-tBu(H)CNAr)(N[Np]Ar)2 (1, Np = neopentyl, Ar = 3,5-C6H3Me2), which functions as a reactive synthon for its tautomer, the three-coordinate, trisamide species Nb(N[Np]Ar)3 (2). Treatment of 1 with various small molecules has demonstrated its capacity to effect two-electron reduction chemistry. Most noteworthy is the reaction between 1 and elemental phosphorus (P4), providing in high yield the bridging diphosphide complex (μ2:η2,η2-P2)[Nb(N[Np]Ar)3]2. However, unsaturated organic functionality including nitriles and aldehydes can insert into the Nb−H bond of 1, leaving the niobaziridine ring intact, thus demonstrating that dual pathways of reactivity are available to the niobaziridine−hydride functional group.

The Niobaziridine−Hydride Functional Group: Synthesis and Divergent Reactivity

Reaction of the uranium(III) tris(anilide) complex (THF)U(N[t-Bu]Ar)3 (1, THF = tetrahydrofuran; Ar = 3,5-Me2C6H3) with MN3 (M = Na, [N(n-Bu)4]) results in the formation of the bimetallic diuranium(IV/IV) complexes M[(μ-N)(U(N[t-Bu]Ar)3)2] (M[3]), which feature a single nitride ligand engaged as a linear, symmetric bridge between two uranium centers The stability of the U═N═U core across multiple charge states is illustrated by stepwise chemical oxidation of Na[3] to the diuranium(IV/V) complex (μ-N)(U(N[t-Bu]Ar)3)2 (3) and the diuranium(V/V) complex [(μ-N)(U(N[t-Bu]Ar)3)2][B(ArF)4] {[3][B(ArF)4]; ArF = 3,5-(CF3)2C6H3} M[3], 3, and [3][B(ArF)4] were characterized by NMR spectroscopy, single-crystal X-ray diffraction, and elemental analysis The cyclic voltammogram of 3 reveals two clean, reversible one-electron electrochemical events at E1/2 = −169 and −067 V, assigned to the [3]−/3 and 3/[3]+ redox couples, respectively The X-ray crystal structures of [N(n-Bu)4][3], 3, and [3][B(ArF)4] reveal a line

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Christopher C. Cummins

Papers

Isolation and Structural Characterization of the Terminal Mesityl Azide Complex V(N3Mes)(I)(NRArF)2 and Its Conversion to a Vanadium(V) Imido Complex

Synthesis of zinc sulfide and cadmium sulfide within ROMP block copolymer microdomains

A cycle for organic nitrile synthesis via dinitrogen cleavage.

The Niobaziridine−Hydride Functional Group: Synthesis and Divergent Reactivity

Uranium-nitrogen multiple bonding: isostructural anionic, neutral, and cationic uranium nitride complexes featuring a linear U=N=U core.