Abstract
dynamic Jahn-Teller distortions of a 3E ground state, tungstenocene bears a closer resemblance to the orbitally nondegenerate metallocenes. Both metallocenes exhibit intense charge-transfer bands in the near-W, but tungstenocene shows an additional sharp electronic transition at -3240 cm-', which is assigned to a transition between two spin-orbit substates. We conclude that Jahn-Teller activity of tungstenocene is quenched by spin-orbit coupling. A substantial fraction of the expelled ligands CO and C2H4 stays within the same matrix cage as the metallocene, resulting in mutual perturbation of IR and UV spectra. On annealing these expelled ligands diffuse away without recombining. However, both heavy metallocenes (M = Mo, W) react thermally with CO in the 50-65 K region in a Xe matrix. All the group 6 metallocenes react photochemically with CO to give the carbonyls MCp2C0. Acknowledgment. We are grateful to Drs. P. A. Cox, A. J. Downs, and M. L. H. Green for many discussions and for 21, 3657-3661 3657
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