Copper(I/II) and cobalt(II) coordination chemistry of relevance to controlled radical polymerization processes

Ulrich Baisch (1) , Rinaldo Poli (1)

1 LCC - Laboratoire de chimie de coordination

The reaction of various alkyl halides (1-bromoethylbenzene, BEB; 1-chloroethylbenzene, CEB; methyl iodide; 1-bromoethylacetate, BEA; and ethyl-2-bromopropionate, EBP) with CuBr/L (L = bipy, Me6TREN) has been investigated in the presence of [Co(acac)2] or [Co(acac)2]/py, with the goal of generating radicals by halogen atom transfer to CuI for subsequence trapping by CoII and generation of an alkylcobalt(III) product. No evidence for the formation of the target product has been obtained. The various reactions, carried out under different conditions, have led to the crystallization of the following compounds: {[Cu(bipy)2Br]+}2{[Cu2Br4]2−} (1); [Cu(Me6TREN)Br]Br; [Cu(Me6TREN)Br0.37Cl0.63]Br (2); trans-[Co(acac)2(THF)2] (3); [Co(Me6TREN)Br]Br (4); [Cu(Me7TREN)I]{[Cu2I2(Br0.628I0.372)2]0.9[I]0.2} (5); [C6H8N]2[CoI4] (6); [Co(acac)3]; and [Co(acac)2(THF)2CoBr2] (7). The structures of 1–7 have been determined by single-crystal X-ray diffraction.

Mots clés: Coordination chemistry; Cobalt; Copper; Me6TREN ligand; Controlled radical polymerization

Domaines: Chimie de coordination

Ulrich Baisch, Rinaldo Poli. Copper(I/II) and cobalt(II) coordination chemistry of relevance to controlled radical polymerization processes. Polyhedron, 2008, 27 (9-10), pp.2175-2185. ⟨10.1016/j.poly.2008.03.022⟩. ⟨hal-03192577⟩