Structural Evidence of the Epoxide Oxygen Propensity to Double Coordination

Diorgano-gallium and -indium complexes with N-heterocyclic carboxylic acids: Synthesis, characterization and structures of [Me2M(O2C–C5H4N)]2, M=Ga or In

“…A similar polymeric structure has been reported recently for [Et 2 In(O 2 C-C 6 H 4 NH 2 -2)] n [9]. This molecule comprises an extended one-dimensional chain containing a diethylindium moiety chelated asymmetrically by the carboxylate group and one of the oxygen atoms bridges the next indium atom in the chain; the NH 2 group does not participate in coordination [9]. The complex [Bu 2 In(O 2 CEt)] n , on pyrolysis, yields indium oxide thin films [10].…”

“…By contrast, diorgano-indium acetates, [R 2 In(OAc)] 1 (R = Me or Et) are polymeric in which the indium atoms are six-coordinated and are bonded to two approximately trans alkyl groups and four oxygen atoms [7,8]. A similar polymeric structure has been reported recently for [Et 2 In(O 2 C-C 6 H 4 NH 2 -2)] n [9]. This molecule comprises an extended one-dimensional chain containing a diethylindium moiety chelated asymmetrically by the carboxylate group and one of the oxygen atoms bridges the next indium atom in the chain; the NH 2 group does not participate in coordination [9].…”

“…Among anionic oxo ligands, both single and internally functionalized alkoxides have been extensively studied and several of them have been employed as catalysts and also as molecular precursors for MOCVD [3,4]. Unlike alkoxides, organo-gallium and -indium carboxylates are relatively under explored [5][6][7][8][9][10][11] and when studied, investigations were limited to simple carboxylic acids. The complexes [R 2 Ga(O 2 CR 0 )] 2 (R = Me, Et, Bu t ; R 0 = Me, Et, Ph, C 6 H 4 CN-3, C 6 H 4 Br-3) are centrosymmetric dimers in which two ''R 2 Ga'' units are bridged by two carboxylate groups [5,6].…”

Ring-opening of 2,3-epoxy-1-propanol with R3Al: Unprecedented regiochemical switching simply achieved by changing alkyl substituents of aluminium reagent

“…Moreover, our recent results also allow for better understanding of factors controlling the formation and redistribution of products in the reaction involving hydroxy organic compounds bearing Lewis base termini and two or more equivalents of R 3 Al [7]. I As a part of our investigations of the epoxides chemistry [6,8], here we report on reactions of epol-H with R 3 Al (R = Me, Et or i Bu) and demonstrate for the first time that the regiochemical switching in the substitution 0022-328X/$ -see front matter Ó…”

“…We have recently initiated systematic studies on the selective alkyl addition to 2,3-epoxy alcohols choosing the group 13 metal alkyls and rac-2,3-epoxy-1-propanol (epol-H) as a simple model system. For example, investigations involving the reaction between epol-H and Me 3 Ga have succeeded in the isolation and structure characterization of the first example of group 13 metal-epoxide complex I [6], which may mimic a potential intermediate complex in the ringopening transformations mediated by aluminium alkyls. Moreover, our recent results also allow for better understanding of factors controlling the formation and redistribution of products in the reaction involving hydroxy organic compounds bearing Lewis base termini and two or more equivalents of R 3 Al [7].…”