Spin-Orbit Mixing and Nephelauxetic Effects in the Electronic Spectra of Nickel(II)-Encapsulating Complexes Involving Nitrogen and Sulfur Donors.
A study of spin-orbit mixing and nephelauxetic effects in the electronic spectra of nickel(II)-encapsulating complexes involving mixed nitrogen and sulfur donors is reported. As the number of sulfur donors is systematically varied through the series [Ni(N(6)(-)(x)()S(x)())](2+) (x = 0-6), the spin-forbidden (3)A(2g) --> (1)E(g) and (3)A(2g) --> (1)A(1g) transitions undergo a considerable reduction in energy whereas the spin-allowed transitions are relatively unchanged. The [Ni(diAMN(6)sar)](2+) and [Ni(AMN(5)Ssar)](2+) complexes exhibit an unusual band shape for the (3)A(2g) --> (3)T(2g) transition which is shown to arise from spin-orbit mixing of the E spin-orbit levels associated with the (1)E(g) and (3)T(2g) states. A significant differential nephelauxetic effect also arises from the covalency differences between the t(2g) and e(g) orbitals with the result that no single set of Racah B and C interelectron repulsion parameters adequately fit the observed spectra. Using a differential covalency ligand-field model, the spectral transitions are successfully reproduced with three independent variables corresponding to 10Dq and the covalency parameters f(t) and f(e), associated with the t(2g) and e(g) orbitals, respectively. The small decrease in f(t) from unity is largely attributed to central-field covalency effects whereas the dramatic reduction in f(e) with increasing number of sulfur donors is a direct consequence of the increased metal-ligand covalency associated with the sulfur donors. Covalency differences between the t(2g) and e(g) orbitals also result in larger 10Dq values than those obtained simply from the energy of the (3)A(2g) --> (3)T(2g) spin-allowed transition.
Stranger
Robert
R
Department of Chemistry, Faculties, The Australian National University, Canberra, ACT 0200, Australia, Centre for Magnetic Resonance and Department of Chemistry, The University of Queensland, Brisbane, QLD 4072, Australia, and School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia.
McMahon
Katie L.
KL
Gahan
Lawrence R.
LR
Bruce
James I.
JI
Hambley
Trevor W.
TW