By Mellor J.W.
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Extra resources for A Comprehensive Treatise Inorganic and Theoretical Chemistry
Using molecular term symbols, the electrothe transition is ðeg Þ4 ! ðeg Þ3 ðt1u nic transitions in cubic symmetry are as follows (114): A B C D 1 A1g ! 3 T1u (spin–orbit allowed) A1g ! ð3 Eu þ 3 T2u Þ (spin–orbit and vibration allowed) 1 A1g ! 1 T1u (dipole allowed, multiplet due to Jahn–Teller effect) 1 A1g ! 1 T1u ; ðdipole allowedÞ; 1 A1g ! 3 T 1u ; 1 A1g ! 3 T 2u (spin–orbit allowed) 1 The interpretation used to explain the absorption spectra of Tl(I) and Pb(II) solid-state complexes can also be extended to aqueous solution spectra of Pb(II) complexes (Fig.
CLAUDIO ET AL. Figure 8. Lead-207 NMR chemical shifts of selected lead compounds referenced to Pb(NO3 )2 (0 ppm). Lead chemical shifts can cover a range of $16,000 ppm and are very sensitive to the lead coordination environment. The lead resonance tends to shift upfield as the electronegativity of the ligand atom increases (S > N > O). [Reprinted with permission from E. S. Claudio, M. A. ter Horst, C. E. Forde, C. L. Stern, M. K. Zart, and H. A. Godwin, Inorg. , 39, 1391–1397 (2000). ] sensitive to the type of donor atoms surrounding the lead ion (Fig.
Further rigorous theoretical studies must be conducted, however, to confirm this hypothesis. The typical absorption spectrum for a leadthiolate complex in a protein consists of two bands, an intense peak near 250 nm and a smaller peak near 340 nm. These bands are characteristic of CT transitions both in position and in their extinction coefficients. Based on comparisons to the doped alkali halides, these bands are likely derived both from intraatomic transitions from the Pb(II) 6s orbital to the Pb(II) 6p orbital and from interatomic CT transitions between mixed s and p orbitals with both metal and ligand character.
A Comprehensive Treatise Inorganic and Theoretical Chemistry by Mellor J.W.