Abstract
The e.s.r. spectra have been obtained from frozen solutions of some Group IV and Group V derivatives of titanocene. All the complexes have an intermediate g-component of 1·988 ± 0·006, and it is postulated that this value is associated with the cyclopentadienyl groups, whilst the low g-value is connected with the remaining ligands. The trends in Aiso(Ti) and g(average) are explained in terms of the electron-donor character of the ligands and the resulting s-orbital expansion. Spin-polarisation is believed to be the dominant mechanism for the aquisition of spin by the ligands, although for the Group V derivatives this negative spin density is reduced by direct overlap between the lone-pair orbitals and the titanium 3dz2 orbital containing the unpaired electron.
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