Aryl C−H Bond Amination by an Electrophilic Diruthenium Nitride

Abstract

Thermolysis of the terminal azido Ru(2)(D(3,5-Cl(2))PhF)(3)N(3) (3, D(3,5-Cl(2))PhF = N,N'-bis(3,5-dichlorophenyl) formamidinate) cleanly produces Ru(2)[(D(3,5-Cl(2))PhF)(3)(D(3,5-Cl(2)-2-NH)PhF)] (4), which is proposed to result from insertion of a nitrido N atom into a ligand aryl C-H bond. This mechanism is supported by differential scanning calorimetry and thermogravimetric analysis results, which show the two-step reaction to be exothermic by -215 kJ mol(-1), in agreement with results from density functional theory calculations. This is the first example of electrophilic insertion of a terminal nitride into an aromatic C-H bond.

Evidence for a One‐Electron Mechanistic Regime in Dirhodium‐Catalyzed Intermolecular CH Amination

“…[23] Here, we report an investigation of the electrochemical oxidation of [Rh 2 A C H T U N G T R E N N U N G (esp) 2 ] to its Rh 2 II,III form and show that a) Rh 2 II,III species are catalytically relevant and b) intermolecular CÀH functionalization can occur without iminoiodinane-transfer reagents, validating the oneelectron-mediated mechanistic regime proposed as Regime B in Scheme 1. Significantly, this work opens the door for the future use of cheaper and more atom economical oxidants in catalytic C À H amination.…”

Electronic Structure of Anilinopyridinate-Supported Ru25+ Paddlewheel Compounds

“…To date, the D values of relatively few Ru 2 5+ complexes supported by N , N -donor equatorial ligands have been determined, − in contrast to the many examples of Ru 2 5+ carboxylate compounds that have been examined . The | D | values determined here fall within the range of those for reported compounds (∼50–80 cm –1 ). − Though the sign of D cannot be determined by the methods employed here, we presume these are positive on the basis of the EPR results of all Ru 2 5+ complexes supported by equatorial N,N -donors that have been measured to date. ,,− The (isotropic) g value of 2.03 for 2 determined here compares reasonably well with the frozen solution-state EPR results of g ⊥ = 2.01 and g || = 1.89 ( g iso = 1.97) …”

Bisaryl Diruthenium(III) Paddlewheel Complexes: Synthesis and Characterization

“…The discovery of Ru 2 (ap) 4 (C 2 Ph) (ap = 2-anilinopyridinate) by Cotton and Chakravarty has inspired extensive investigation of the organometallic chemistry of di- and triruthenium paddlewheel complexes bearing axial mono- and bisalkynyls, − and their potential applications as molecular wires in electronic devices have been explored by our laboratory. − In addition to Ru 2 alkynyls, other aspects of di- and triruthenium compounds vigorously pursued in recent years include C–H activation, aerobic and peroxy oxidation catalysis, − magnetism, − and devices based on metal strings. , …”