Syntheses And Structures Of Organic-Tellurium Halides And Diphenyl-Tellurium Oxide Copper(Ⅱ)/Manganese(Ⅲ) Complexes

A series of novel organic-tellurium halides with supermolecular hydrogen bond and diphenyl-tellurium oxide copper（II）/manganese（III）complexes were synthesized by reactions of diaryl tellurides with hydrogen chloride（1.0 mol/L）,ammonium chloride（saturated,7.0 mol/L）,bromine（1.0 mol/L）,copper chloride dihydrate and manganese chloride tetrahydrate,respectively,in the thesis.Treatment of diphenyl tellurium Ph₂Te with aqueous hydrogen chloride in refluxing tetrahydrofuran gave an organotellurium chloride trans-[（Ph₂Te）（μ-Cl）₂]_n（1）,whereas interaction of diphenyl tellurium Ph₂Te with ammonium chloride under a similar condition afforded an organotellurium chloride cis-[（Ph₂Te）（μ-Cl）₂]_n（2）.Reaction of di-p-methylphenyl tellurium（p-MeC₆H₄）₂Te and bromine in refluxing tetrahydrofuran resulted in formation of an organotellurium bromide[（p-MeC₆H₄）₂TeBr₂]（3）with a step-like tetrameric structure,which further reacted with sodium hydroxide in refluxing tetrahydrofuran to give a dinuclear tellurium oxide[{（p-Me-C₆H₄）₂TeBr}₂（μ-O）]（4）with a bridging oxygen atom.Treatment of di-p-methylphenyl tellurium（p-MeC₆H₄）₂Te with sodium hydroxide in ethylene glycol gave dinuclear tellurium oxide[（p-MeC₆H₄）₂Te]₂[C（CH₂）₂CH₃]₄（μ-O）₄（5）.Diphenyl-tellurium oxide copper（II）complex[Cu^II（Ph₂TeO）₄]Cl₂?2CH₃CN（6）with a square-planar geometry was isolated by the reaction of copper chloride dihydrate and diphenyl tellurium oxide Ph₂TeO in the refluxing acetonitrile.The solid copper（II）complex was further refluxed in the dichloromethane to lead to isolation of a planar copper（II）complex[Cu^II（Ph₂TeOCH₂）₄]Cl₂?2CH₃CN?2HCN（7）,with methylene bridging diphenyl tellurium oxide.Reaction of manganese chloride tetrahydrate with diphenyl tellurium oxide in molar ratio of 1:4 in a mixture of methanol and acetonitrile（v:v=1:2）afforded the maganese（III）complex of[Mn^IIICl（Ph₂TeO）₄]Cl₂（8）with distorted square pyramidal.Molecular structures of complexes 1⁸ were unambiguously established by single-crystal X-ray crystallography.