Cooperative Effects of Aniline with DMSO in Ru^II Complexes: Tuning the Reactivity for Ring‐Opening Metathesis Polymerization

Abstract

The complex cis,fac-[RuCl 2 (DMSO-O)(DMSO-S) 3 ] [1] reacted with aniline (NH 2 Ph) under reflux to produce the complex trans,cis,cis-[RuCl 2 (DMSO-S) 2 (NH 2 Ph) 2 ] [2], whereas at room temperature the resulting complex was cis,fac-[RuCl 2 (DMSO-S) 3 (NH 2 Ph)] [3]. The complexes were characterized by FTIR, EPR, 1 H and 13 C NMR, electronic spectra, and the crystal structure of 2 was determined by single X-ray crystallography. The influence of NH 2 Ph and DMSO as ancillary ligands in the new complexes was then evaluated for ring-opening metathesis polymerization (ROMP) of norbornene (NBE), norbornadiene (NBD), and dicyclopentadiene (DCPD) in presence of ethyl [a]

Dual catalytic performance of arene‐ruthenium amine complexes for norbornene ring‐opening metathesis and methyl methacrylate atom‐transfer radical polymerizations

“…In our research group, noncarbene ruthenium-based complexes have been studied for ROMP and ATRP. [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40] Many of these compounds have exhibited good activity, forming polymers and copolymers in high yields, with different thermal and morphological characteristics. Among these precatalysts, ruthenium amine compounds have produced polymers from norbornene (NBE) and norbornadiene (NBD) by ROMP and controlled methyl methacrylate (MMA) and styrene (St) polymerization via ATRP.…”

“…Ruthenium complexes bearing p ‐cymene with different types of ligands such as phosphines, Schiff bases, and N ‐heterocyclic carbenes with a general formula of [RuCl 2 ( p ‐cymene)(L)] have been investigated as ROMP or ATRP catalysts. In our research group, noncarbene ruthenium‐based complexes have been studied for ROMP and ATRP . Many of these compounds have exhibited good activity, forming polymers and copolymers in high yields, with different thermal and morphological characteristics.…”

Amino complexo de Ru-dmso como pré-catalisador para reação de polimerização: estudo cinético e mecanístico

“…propriedades térmicas e morfologia. (BORIM et al, 2016;CARVALHO JR.;FERNANDES et al, 2020FERNANDES et al, , 2015FONSECA et al, 2015;MARTINS et al, 2019;MATOS;LIMA-NETO, 2006;SÁ et al, 2010 O espectro de RMN 1 H da mistura reacional de [RuSdmap] com EDA (Figura 44) foi adquirido utilizando os seguintes parâmetros: varreduras, 128; ganho do receptor, 28 (receiver gain); RD relaxação, 3 s (relaxation delay); amplitude do pulso 8,5 (pulse width) e tempo de aquisição, 5,0176 s (acquisition time).…”