A MIXED-VALENCE ((TITIIV)-TI-III) CARBOXYLATE COMPLEX - CRYSTAL-STRUCTURES AND PROPERTIES OF [TI2OCL3(O(2)CPH)(2)(THF)(3)] AND [NET(4)](3)[TI2CL9]

The reaction of [TiCl3(thf)(3)] with 4 equiv. of PhCO(2)H in refluxing thf or 3 equiv. of Cl- in CH2Cl2 gives [Ti2OCl3(O(2)CPh)(2)(thf)(3)] 1 and [NEt(4)](3)[Ti2Cl9] 2, respectively: crystallography shows them to possess trapped-valence [Ti-2(mu-O)(mu-O(2)CPh)(2)](3+) ((TiTIV)-T- III) and [Ti-2(mu l)(3)](3+) cores, respectively, the former with an u nusual asymmetrically bridging O2- displaying triple/single bond dista nces to the metal ions.