Transition metals Fenske-Hall molecular orbitals

Its absorption spectrum shows one band at 320 nm (e = 2900 M 1cm 1), assigned to the cti - ct2 transition localized in the Au-Tl moiety. The emission spectrum in the solid state at 77 K shows a band at 602 nm, which is attributable to a transition between orbitals that appear as a result of the metal-metal interaction. In this sense, Fenske-Hall molecular orbital calculations indicate that the ground state is the result of the mixing of the empty 6s and 6pz orbitals of gold(I) with the filled 6,v and the empty 6pz orbitals of thallium(I). In frozen solution, this derivative shows a shift of the emission to 536 nm, which has been explained by a higher aggregation of [AuT1(MTP)2] units in the solid state if compared to the situation in solution. 

The results of Fenske-Hall molecular orbital calculations for transition metal thiophene complexes with the ligand bound in 1)5, T l-S-bound, 1)2,1 4 t 4-S-112 and ring-opened modes have been reported335. Formation of Ti -complexes such as [Cp Ir(Ti4-2,5-diinethylthiophene)]2+ was found to be favoured by the presence of elecron-rich metal centres and also to lead to activation of the ring with respect to a ring-opening reaction via a formal oxidative addition reaction. 

F. Fenske. We demonstrate for transition metal complexes that the non-empirical Fenske-Hall (FH) approach provides qualitative results that are quite similar to the more rigorous treatment given by density functional theory (DFT) and are quite different from Hartree-Fock-Roothaan (HFR) calculations which have no electron correlation. For example, the highest occupied molecular orbital of ferrocene is metal based for both DFT and FH while it is ligand (cyclopentadienyl) based for HFR. In the doublet (S = 1/2) cluster, Cp2Ni2(pi-S)2(MnCO)3, the unpaired electron is delocalized over the complex in agreement with the DFT and FH results, but localized on Mn in the HFR calculation. A brief description of the theory of FH calculations is used to rationalize the origin of its similarity to DFT. 

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