An argon matrix effect on the geometry and infrared spectrum of the agostic complex H_{2}C=TiHF was simulated within the framework of IEF-PCM at the B3LYP and BPW91 levels. The matrix effect simulations indicate that the complex may take on a pyramidal rather than a planar structure when it is isolated in an argon matrix. The agostic interaction of the complex seems slightly weakened upon the modeling. Molecular structure of the complex becomes more pyramidal upon the matrix effect modeling in order to increase the dipole moment of the complex. The variation of the agostic interaction is not a cause but a consequence of the geometric variation. The infrared frequencies simulated by the IEF-PCM are in better agreement with the experimental values than those without the matrix effect modeling. |
full paper (pdf, 656 Kb)