Chemical applications of topology and group theory. 34. Structure and bonding in titanocarbohedrene cages.

Abstract

Chemical bonding models are developed for the titanocarbohedrenes Ti14C13 and Ti8C12 by assuming that the Ti atoms use a six-orbital sd5 manifold and there is no direct Ti...Ti bonding. In the 3 x 3 x 3 cubic structure of Ti14C13, the 8 Ti atoms at the vertices of the cube are divided into two tetrahedral sets, one Ti(III) set and one Ti(IV) set, and the 6 Ti atoms at the midpoints of the cube faces exhibit square planar TiC4 coordination with two perpendicular three-center four-electron bonds. The energetically unfavorable Th dodecahedral structure for Ti8C12 has 8 equivalent Ti(III) atoms and C2(4-) units derived from the complete deprotonation of ethylene. In the more energetically favorable Td tetracapped tetrahedral structure for Ti8C12, the C2 units are formally dianions and the 8 Ti atoms are partitioned into inner tetrahedra (Ti(i)) bonded to the C2 units through three-center Ti-C2 bonds and outer tetrahedra (Ti degrees) bonded to the C2 units through two-center Ti-C bonds. The Ti atoms in one of the Ti4 tetrahedra are Ti(0) and those in the other Ti4 tetrahedron are Ti(III). Among the two such possibilities, the lower energy form has the (Ti0)o4(Ti(III))i4 configuration, corresponding to dicarbene C2 ligands with two unpaired electrons in the carbon-carbon pi-bonding similar to the multiple bond in triplet O2. This contrasts with the opposite (Ti(III)o4(Ti0)i4 configuration in the higher energy form of Th-Ti8C12, corresponding to ethynediyl ligands with full C...C triple bonds and unpaired electrons in the C sp hybrid orbitals for sigma-bonding to Ti.