C–H Activation of π-Arene Ruthenium Complexes

TY - JOUR

T1 - C–H Activation of π-Arene Ruthenium Complexes

AU - Wilkinson, Luke Alexander

AU - Pike, Jack

AU - Walton, James

PY - 2017/11/27

Y1 - 2017/11/27

N2 - We present a C–H activation protocol for aromatic compounds that overcomes the current limitations of the need for a directing group or covalently bound activating groups, by exploiting the increase in C–H acidity of aromatic compounds on π-coordination to a Ru(II) center. The increased acidity facilitates catalytic concerted metalation–deprotonation and subsequent arylation reactions. We present the development and optimization of the C–H activation protocol and show the applicability of the reaction to a range of aromatic substrates, including the simplest of substrates (benzene). Furthermore, we demonstrate the recyclability of the activating Ru(II) fragment using photolysis and give a mechanistic study, which provides strong evidence that this reaction occurs via a silver-mediated C–H bond activation. This is the first time Ru complexes have been shown to allow C–H activation of arenes by a π-coordination mechanism.

AB - We present a C–H activation protocol for aromatic compounds that overcomes the current limitations of the need for a directing group or covalently bound activating groups, by exploiting the increase in C–H acidity of aromatic compounds on π-coordination to a Ru(II) center. The increased acidity facilitates catalytic concerted metalation–deprotonation and subsequent arylation reactions. We present the development and optimization of the C–H activation protocol and show the applicability of the reaction to a range of aromatic substrates, including the simplest of substrates (benzene). Furthermore, we demonstrate the recyclability of the activating Ru(II) fragment using photolysis and give a mechanistic study, which provides strong evidence that this reaction occurs via a silver-mediated C–H bond activation. This is the first time Ru complexes have been shown to allow C–H activation of arenes by a π-coordination mechanism.

U2 - 10.1021/acs.organomet.7b00563

DO - 10.1021/acs.organomet.7b00563

M3 - Article

SN - 0276-7333

VL - 36

SP - 4376

EP - 4381

JO - Organometallics

JF - Organometallics

IS - 22

ER -