Synthesis, Structure, and Reactivity of O-Donor Ir(III) Complexes:  C−H Activation Studies with Benzene

Abstract

Table S1. Line-Broadening Analysis.The mononuclear-dinuclear equilibrium was measured in the slow exchange region from the width of the NMR signals at half height using eq: 1/ τ a = π(ω A -ω˚A) where τ a is the residence time in site A and ω A and ω˚A are the linewidths in the presence and in the absence of exchange, respectively. ω˚A was measured at a temperature where molecule was non exchanging in the NMR time scale. The experimental line widths were corrected by subtracting the line width of TMS to minimize the effect of instrumental linebroadening.

Cyclometalated Iridium(III) Complexes with Ligand Effects on the Catalytic C–H Bond Activation of Toluene

“…This complex showed a better performance for CHA than low‐valent iridium complexes . Until now, the use of the Ir III complex for CHA has rarely been reported , . In other fields, Ir III complexes with bidentate ligands, including carbon–nitrogen (C ^ N), nitrogen–oxygen (N ^ O), and nitrogen–nitrogen (N ^ N) ligands, have been widely applied in organic light‐emitting diodes (OLEDs),, biolabeling,, dye‐sensitized solar cells (DSCs),, and the photoreaction of water;, most of the bidentate ligands wereeasily prepared and have a stable bond to the metal center.…”

Nickel-Catalyzed Anti-Markovnikov Hydroarylation of Unactivated Alkenes with Unactivated Arenes Facilitated by non-Covalent Interactions

“…The reaction of t-butylethylene (14) with benzene occurred in nearly quantitative yield after only 1 h under the standard conditions ( Fig. 2C, Entry 1).…”

“…1A). Iridium, ruthenium and platinum systems reported by Perriana, [11][12][13][14] Gunnoe, [15][16] and Goldberg, 17 all catalyze the reaction of benzene (1) with propylene (2) to provide alkylarenes 3 and 4 with moderate activity, but to give nearly 1:1 ratios of constitutional isomers (Fig. 1B).…”

Oxidative Alkenylation of Arenes Using Supported Rh Materials: Evidence that Active Catalysts are Formed by Rh Leaching

“… [14,16–20] These potential advantages include: a) direct arene alkenylation (rather than alkylation) via β‐hydride elimination after the olefin insertion step, b) selective production of 1‐aryl alkane/alkene by circumventing carbocationic intermediates that lead to Markovnikov selectivity, c) conversion of electron‐deficient arenes, d) new regioselectivity for alkenylation or alkylation of substituted arenes, and e) inhibition of polyalkylation since alkylated or alkenylated products can be less reactive than starting arenes [14] . Molecular catalysts involving Ni, Ir, Ru, Pt, Pd and Rh have been studied for catalytic C−H alkylation or alkenylation of arenes with α‐olefins [15,16,21–35] …”

“…[14] Molecular catalysts involving Ni, Ir, Ru, Pt, Pd and Rh have been studied for catalytic CÀ H alkylation or alkenylation of arenes with α-olefins. [15,16,[21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Recently, we reported Rh-catalyzed arene alkenylation to directly synthesize styrene and 1-aryl alkenes using molecular catalysts in homogeneous processes. [13,14,[36][37][38][39][40][41] Based on the mechanistic studies, our initial proposed catalytic cycle involves (Scheme 3): a) Rh-carboxylate assisted arene CÀ H activation, b) ethylene coordination and insertion into a Rh-aryl bond, c) βhydride elimination, and d) alkenyl arene dissociation and oxidation of a RhÀ H intermediate with CuX 2 (X = carboxylate) to regenerate the starting catalyst.…”