Rhodium and iridium complexes of N-heterocyclic carbenes (3a-c and 4a-c) were obtained by transmetalation from the corresponding Ag(I) complexes. The structure of 3b was verified by X-ray diffraction. The compounds display restricted rotation about the metal-carbene bond, the rate of which can be controlled by altering the steric bulk of the auxiliary ligands. Infrared spectroscopy provides an estimate of the electron-donor power of the carbene ligands from ν(CO) of the carbonyl derivatives.

Rhodium(III)-catalyzed direct functionalization of C-H bonds under oxidative conditions leading to C-C, C-N, and C-O bond formation is reviewed. Various arene substrates bearing nitrogen and oxygen directing groups are covered in their coupling with unsaturated partners such as alkenes and alkynes. The facile construction of C-E (E = C, N, S, or O) bonds makes Rh(III) catalysis an attractive step-economic approach to value-added molecules from readily available starting materials. Comparisons and contrasts between rhodium(III) and palladium(II)-catalyzed oxidative coupling are made. The remarkable diversity of structures accessible is demonstrated with various recent examples, with a proposed mechanism for each transformation being briefly summarized (critical review, 138 references).

The possibility of developing new methods for the efficient construction of organic molecules via disconnections other than traditional functional group transformations has driven the interest in direct functionalization of C-H bonds. The ubiquity of C-H bonds makes such transformations attractive, but they also pose several challenges. The first is the reactivity and selectivity of C-H bonds. To achieve this, directing groups (DGs) are often installed that can enhance the effective concentration of the catalyst, leading to thermodynamically stable metallacyclic intermediates. However, the presence of a pendant directing group in the product is often undesirable and unnecessary. This may account for the limitation of applications of C-H functionalization reactions in more common and general uses. Thus, the development of removable or functionalizable directing groups is desirable. Another key problem is that the reactivity of the resulting M-C bond can be low, which may limit the scope of the coupling partners and hence limit the reaction patterns of C-H activation reactions. While the first Cp*Rh(III)-catalyzed C-H activation of arenes was reported only 7 years ago, significant progress has been made in this area in the past few years. We began our studies in this area in 2010, and we and others have demonstrated that diversified catalytic functionalization of arenes can be realized using Cp*Rh(III) complexes with high reactivity, stability, and functional group compatibility. This Account describes our efforts to solve some of these challenges using Rh(III) catalysis. We fulfilled our design and activation of the arene substrates by taking advantage of the nucleophilicity, electrophilicity, oxidizing potential, and properties of a participating ligand of the directing groups when the arenes are coupled with relatively reactive unsaturated partners such as alkenes and alkynes. These in situ funtionalizable roles of the DG allowed extensive chemical manipulation of the initial coupled product, especially in the construction of a diverse array of heterocycles. In the coupling of arenes with polar coupling partners, the polar Rh(III)-C(aryl) bond showed higher reactivity as both an organometallic reagent and a nucleophilic aryl source. The polar coupling partners were accordingly activated by virtue of umpolung, ring strain, and rearomatization. All of these transformations have been made possible by integration of the higher reactivity, stability, and compatibility of Rh(III)-C bonds into catalytic systems. We have demonstrated that to date some of these transformations can be achieved only under rhodium catalysis. In addition, by means of stoichiometric reactions, we have gained mechanistic insights into the interactions between the Rh-C bond and the other coupling partners, which have opened new avenues in future direct C-H functionalization reactions.

Hierarchical sulfonated graphene nanosheet/carboxylated multiwalled carbon nanotube/polyaniline (sGNS/cMWCNT/PANI) nanocomposites were synthesized through an interfacial polymerization method. Activated porous graphene (aGNS) was prepared by combining chemical foaming, thermal reduction, and KOH activation. Furthermore, we have successfully fabricated an asymmetric supercapacitor (ASC) using sGNS/cMWCNT/PANI and aGNS as the positive and negative electrodes, respectively. Because of its unique structure, high capacitive performance, and complementary potential window, the ASC device can be cycled reversibly at a cell voltage of 1.6 V in a 1 M H2SO4 aqueous electrolyte, delivering a high energy density of 20.5 Wh kg(-1) at a power density of 25 kW kg(-1). Moreover, the ASC device also exhibits a superior long cycle life with 91% retention of the initial specific capacitance after 5000 cycles.

An overview of reactive gold α-oxo carbenoid intermediates in the gold-catalyzed functionalization of alkynes is presented. Such intermediates can be generated from inter- and intramolecular oxidation of alkynes by nucleophilic oxygen-atom donor groups, such as amine N-oxides, pyridine N-oxides, nitrones, nitro compounds, sulfoxides, and epoxides. These O-atom transfer processes occur by gold-mediated addition-elimination reactions. In catalytic systems, α-oxo carbenoids can undergo nucleophilic attack by imine, arene, and migrating hydride as well as alkyl groups, leading to cascade reactions and the construction of new skeletons. The facile construction of C-E (E=C, N, S, or O) bonds makes it an attractive step-economic approach to value-added molecules from readily available starting materials. The scope, mechanisms, and reactivity of such α-oxo carbenoid species are discussed. The remarkable diversity of structures accessible is demonstrated with various recent examples.

An efficient Rh(III)- and Ir(III)-catalyzed, chelation-assisted C-H alkynylation of a broad scope of (hetero)arenes has been developed using hypervalent iodine-alkyne reagents. Heterocycles, N-methoxy imines, azomethine imines, secondary carboxamides, azo compounds, N-nitrosoamines, and nitrones are viable directing groups to entail ortho C-H alkynylation. The reaction proceeded under mild conditions and with controllable mono- and dialkynylation selectivity when both mono- and dialkynylation was observed. Rh(III) and Ir(III) catalysts exhibited complementary substrate scope in this reaction. The synthetic applications of the coupled products have been demonstrated in subsequent derivatization reactions. Some mechanistic studies have been conducted, and two Rh(III) complexes have been established as key reaction intermediates. The current C-H alkynylation system complements those previously reported under gold or palladium catalysis using hypervalent iodine reagents.

Enantiomeric access to pentatomic biaryls is challenging due to their relatively low rotational barrier. Reported herein is the mild and highly enantioselective synthesis of 2,3′-biindolyls via underexplored integration of C−H activation and alkyne cyclization using a unified chiral Rh(III) catalyst. The reaction proceeded via initial C−H activation followed by alkyne cyclization. A chiral rhodacyclic intermediate has been isolated from stoichiometric C−H activation, which offers direct mechanistic insight.

[reaction: see text] Iridium(III) hydrides prove to be air-stable active catalysts for intramolecular hydroalkoxylation and hydroamination of internal alkynes with proximate nucleophiles. The cyclization follows highly selective 6-endo-dig regiochemistry when regioselectivity is an issue.