Effect of Rh(III) and Ru(II) complexes in the polymerization of vinyl monomers initiated by charge transfer mechanism

Abstract

SynopsisThe initiation of polymerization of vinyl monomers such as methyl methacrylate (MMA) and methyl acrylate (MA) by a charge transfer complex formed between n-butylamine(nBA) and carbon tetrachloride (CCl4) in dimethylsulfoxide (DMSO) at 3OoC is slow. The effect of the dimethylsulfoxide complexes of Rh(II1) and Ru(I1) on the polymerization of MMA and MA in the presence of nBA, and CCl, in DMSO has been studied. The rate of polymerization and percent conversion of the MMA and MA at 3OoC are evaluated at the critical concentration of the metal complexes. At the critical range of the metal complex concentrations, both Rp and percent conversion of MMA and MA were found to be highest. However, above and below the critical concentrations, R, and percent conversion of the monomers were found to decrease. A suitable mechanism for the polymerization has been proposed. EXPERIMENTALMMA(BDH) and MA(BDH) were purified as prescribed in the literature.12 nBA,l3 Ccl4,l4 and DMS015 (all E. Merck) were distilled before use. The complexes hexakis (DMSO) rhodium(II1) tetrafluoroborate {[Rh(DMSO)6] (BF&]) (A), trichlorotris(DMS0) rhodium(III){[Rh(DMS0)~C1~]) (B), tribromotris(DMS0) rhodium(II1) {[Rh(DMS0)3Br3])(C), dichlorotetrakis(DMS0) ruthenium (11) {[Ru(DMS0)4Cl2])(D), and dibromotetrakis(DMS0) ruthenium

The Complexes [OsCl2(azole)2(dmso)2] and [OsCl2(azole)(dmso)3]: Synthesis, Structure, Spectroscopic Properties and Catalytic Hydration of Chloronitriles

“…[4,5] Of the platinum group metals, the most extensively studied appear to be ruthenium-dmso complexes, some of which are endowed with potent antitumour properties [6,7] or have found application in catalytic processes. [8][9][10] In addition, Ru II -dmso complexes have been successfully employed as precursors for the synthesis of a large variety of compounds, and, in particular, of [Ru II Cl 2 (azole) 2 (dmso) 2 ] geometric isomers, [11][12][13][14][15][16] 2 ] species are able to mediate the insertion of the CϵN group of acetonitrile in the N1-H bond of the N2-coordinated indazole, these being the first examples of the metal-assisted iminoacylation of indazole. [17] Comparison of the chemistry of ruthenium(II) dmso complexes with that of osmium(II) dmso species has permitted us to unravel expected similarities between these two types of complexes, but also remarkable, although less pro-the hydration of trichloroacetonitrile to trichloroacetamide and dichloroacetonitrile to dichloroacetamide with high selectivity.…”

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

“…A very exploited precursor is the cis,fac ‐[RuCl 2 (DMSO–O)(DMSO–S) 3 ] [ 1 ] due to its versatility associated with the ambidentate nature of the coordinated S‐/O‐DMSO . DMSO‐based complexes are promising candidates for homogeneous catalysis because ligand replacements occur quite easily and the manipulation procedure does not require extreme O 2 ‐free atmosphere , , . The DMSO molecule is able to act as ancillary ligand in different processes, driving the reaction for specific purpose , , , , .…”

Ruthenium(III) catalysis in polymerization of vinyl monomers by charge‐transfer mechanism with aminoalcohols and carbontetrachloride: A kinetic study

“…The kinetics of polymerization of vinyl monomers initiated by the charge-transfer mechanism in the presence of CCl 4 have been studied by many investigators [6][7][8][9][10][11] and different mechanisms for the reactions have been proposed. Rh III and Ru II complexes have also been reported to accelerate the rate of polymerization of vinyl monomers initiated by the charge-transfer mechanism [12].…”