Charge density analysis of the (C-C)-->Ti agostic interactions in a titanacyclobutane complex.
The experimental electron density study of Ti(C(5)H(4)Me)(2)[(CH(2))(2)CMe(2)] provides direct evidence for the presence of (C-C)-->Ti agostic interactions. In accord with the model of Scherer and McGrady, the C(alpha)-C(beta) bond densities no longer show cylindrical symmetry in the vicinity of the Ti atom and differ markedly from those of the other C-C bonds. At the points along the C(alpha)-C(beta) bond where the deviation is maximal the electron density is elongated toward the metal center. The distortion is supported by parallel theoretical calculations. A calculation on an Mo complex in which the agostic interaction is absent supports the Scherer and McGrady criterion for agostic interactions. Despite the formal d(0) electron configuration for this Ti(IV) species, a significant nonzero population is observed for the d orbitals, the d orbital population is largest for the d(xy) orbital, the lobes of which point toward the two C(alpha) atoms. Of the three different basis sets for the Ti atom used in theoretical calculations with the B3LYP functional, only the 6-311++G** set for Ti agrees well with the experimental charge density distribution in the Ti-(C(alpha)-C(beta))(2) plane.
Scheins
Stephan
S
Department of Chemistry, University of New York at Buffalo, Buffalo, New York 14260, USA.
Messerschmidt
Marc
M
Gembicky
Milan
M
Pitak
Mateusz
M
Volkov
Anatoliy
A
Coppens
Philip
P
Harvey
Benjamin G
BG
Turpin
Gregory C
GC
Arif
Atta M
AM
Ernst
Richard D
RD