Selective Arene Cleavage by Direct Insertion of Iridium into the Aromatic Ring

Abstract

We report an unprecedented selective cleavage of aromatic C À Cb onds through the insertion of well-defined iridium complexes into the aromatic ring of simple alkylarenes. The insertion occurs at 50-100 8 8Cw ithout the activation of weaker CÀHand CÀCbonds and gives unique metallacycles in high yields.K ey to the success of this approach is metalinduced deformation of the arene ring, whichc reates temporary ring strain and promotes direct and selective insertion of the metal into the otherwise inert arene ring CÀCbonds.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

Synthetic Strategy Towards Heterodimetallic Half-Sandwich Complexes Based on a Symmetric Ditopic Ligand

“…Solvents were evaporated under reduced pressure using a rotary evaporator. The precursor complexes [Ru(cym)Cl 2 ] 2 a ( Bennett and Smith, 1974 ), [Rh(Cp * )Cl 2 ] 2 b ( Vogt et al, 2005 ; Nejman et al, 2015 ), [Ir(Cp * )Cl 2 ] 2 c ( Vogt et al, 2005 ; Jakoobi et al, 2017 ) and [Os(cym)Cl 2 ] 2 d ( Peacock et al, 2007 ) were prepared according to literature procedures.…”

Potent Inhibition of Thioredoxin Reductase by the Rh Derivatives of Anticancer M(arene/Cp*)(NHC)Cl2Complexes

“…Deuterated solvents were purchased from Cambridge Isotope Laboratories. Pro-carbenes a and b and the precursors [Rh­(Cp*)­Cl 2 ] 2 , and [Ir­(Cp*)­Cl 2 ] 2 , were synthesized as previously reported.…”

“…Deuterated solvents were purchased from Cambridge Isotope Laboratories. Pro-carbenes a 30 and b 30 and the precursors [Rh(Cp*)Cl 2 ] 2 67,68 and [Ir(Cp*)-Cl 2 ] 2 68,69 were synthesized as previously reported. One-dimensional (1D) ( 1 H, 13 C{ 1 H}, and DEPT-Q) and 2D ( 1 H− 13 C, 1 H− 1 H COSY, HSQC, HMBC, and NOESY) NMR spectra were recorded on Bruker DRX 400 MHz NMR spectrometers at ambient temperature at 399.89 MHz ( 1 H) or 100.55 MHz ( 13 C{ 1 H}) with chemical shifts (δ, ppm) reported relative to the solvent peaks of the deuterated solvents.…”