On the Electronic Structure of Bis(η5-cyclopentadienyl) Titanium

Abstract

Prior to the first reported synthesis of the titanium analogue of ferrocene, bis(η 5 -cyclopentadienyl)Ti, there was theoretical speculation as to the electronic structure of what would become known as titanocene. In time, the original report of a successful synthesis was apparently shown to be incorrect, and a dimeric form of the substance was postulated as the correct structure. In the present work, high level ab initio and DFT calculations are performed on the monomer to help answer these structural questions, and to compare with early theoretical and experimental efforts. The need for a multi-configurational wave function is analyzed and found to be unnecessary. The present calculations predict that the ground state of monomer is a triplet with parallel and freely rotating cyclopentadienyl rings, which further suggests that experimentally synthesized titanocene is indeed some form of the dimer.