Unprecedented Migration of a Methyl Group in 2-(2‘,6‘-Dimethylphenylazo)-4-methylphenol Mediated by Ruthenium

Abstract

An unprecedented chemical transformation of 2-(2',6'-dimethylphenylazo)-4-methylphenol has been observed upon its reaction with [Ru(PPh(3))(2)(CO)(2)Cl(2)] whereby the methyl group at the 2' position migrates to the 4' or 6' position.

Synthesis, structure, catalytic transfer hydrogenation and biological activity of cyclometallated ruthenium(III)2-(arylazo)phenolate complexes

“…The cyclometallation reaction, i.e., the intramolecular activation of aromatic C-H bonds of coordinated ligands by transition metals has been widely studied [1][2][3][4][5]. Conventionally cyclometallation has involved one ligating group holding a metal center close to C-H bond and subsequent closure of the ring via the formation of carbon to metal bond [6,7].…”

Syntheses and Crystal Structures of Ruthenium-Salen Complexes Containing Triphenylphosphine Ligands

“…The sterical crowding around the new sp 3 atoms is relaxed by the V shape of the ligand so that abnormal torsion angles around N(1) and C(2) are avoided. The Ru-P bond length of 2.3447(6)Å is comparable to that in other ruthenium phosphine complexes such as [Ru(2-Br-salen) 2 [3,5-…”

“…Ruthenium complexes are currently investigated because of their interesting structural, electrochemical, catalytic, and biological properties [1][2][3][4][5] including research of ruthenium complexes containing diimino tetradentate Schiff bases, such as salen and salophen ligands [6,7]. It has been noted that manganese-salen complexes can be widely used as catalysts for alkene epoxidation [8].…”

Interaction of 2-(2′,6′-dialkylphenylazo)-4-methylphenols with iridium. C–H activation and migration of alkyl group

“…Metal promoted C-H and C-C bond activation of organic molecules has thus been of significant current interest [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35]. We have been active, for quite some time, in the synthesis of organometallic complexes via platinum-group metal mediated C-H bond activation of organic ligands in general [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53] and of 2-(arylazo)-4-methylphenols (I) in particular [44][45][46][47][48][49], and the present work has emerged from our continued interest in this area. In this study iridium has been selected as the platinum-group metal for promoting C-H or C-C bond activation and [Ir(PPh 3 ) 3 Cl] has been utilized as the iridium starting material.…”