Characterization and thermal activation of adducts of Group 4 tetrahalides with 1,2-dialkoxyalkanes

摘要

Coordination compounds of general formula MX_4[κ ~2-O(R)CH_2CH(R′)OR′′], 2a-i, have been prepared in high yield upon addition of a variety of 1,2-dialkoxyalkanes, ROCH_2CH(R′)OR′′, to MX_4 (M = Ti, X = F, 1a, I, 1b; M = Zr, X = Br, 1c, I, 1d). The new complexes have been characterized by elemental analysis and NMR spectroscopy. The thermal stability of 2 has been studied. Fragmentation of the TiI_4 adducts takes place in chloroform solution at 90 °C: after hydrolysis of the reaction mixtures, MeI and CH_2ICH_2I have been detected from TiI_4[dme] [dme = MeO(CH_2)_2OMe], MeI and Me_2O from TiI _4[MeOCH_2CH(Me)OMe], and MeI, CH_2ICH _2I, Me_2O, CH_2ClI from TiI _4[MeO(CH_2)_2OCH_2Cl]. The diether MeO(CH_2)_2OCH_2Cl is thermally activated also when coordinated to ZrX_4 (X = Br, I): after hydrolysis, MeBr, CH _2BrCH_2Br, O(CH_2CH_2Cl)_2 and Me_2O (X = Br) and MeI, CH_2ClI and CH _2ICH_2I (X = I) have been found, respectively.