Theoretical Inorganic Chemistry by Boschke F.L.

By Boschke F.L.

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9 percent) known in any organic compound. Nyholm and Vrieze t37) preparated rhodium(III) complexes of the ligand HgXtogether with three RaAs and two X - , by replacing a hydride ligand with HgX 2 eliminating HX. In a certain sense, this ligand exemplifies the oxidation state mercury(O) isoelectronic with thallium(I). It may be stretching the analogy a little too far to argue that the dimeric mercurous ion Hg~2 is the complex of Hg§ with a mercury atom having equilibrated their electronic density to become symmetric.

Even considering the fact that several transitions coincide in the copper(II) complexes (it is recognized 76' 77) that the shoulder is due to the excitation of one electron from (3 z 2 - r 2) to the available empty position in (x 2 - y 2 ) and the maximum to excitation of (xz, yz) degenerate in systems with two equivalent Cartesian axes x and y , and of (xy) to this hole in (x 2 - y 2 ) whereas species such as Cu(NHa)4(H20) +2 apparently presenting one, somewhat asymmetric band have all these transitions almost coinciding) it would be difficult to explain a factor higher than 2 as the intensity ratio between Cu(II) and Ni(II) with the same ligands.

Actually, since 6 is somewhat larger, eo of Eq. (21) is lower for X = C1. 3 9 10 - a for Cu(NH3)~ 2 having a spectrum of the same form cannot be explained exclusively from the denominator in Eq. (22). Thus, the first electron transfer bands are situated approximately at 50000 c m - t in the Cu(II) aqua ion and at 60000 cm-1 in Ni(H20)~ 2 . Even considering the fact that several transitions coincide in the copper(II) complexes (it is recognized 76' 77) that the shoulder is due to the excitation of one electron from (3 z 2 - r 2) to the available empty position in (x 2 - y 2 ) and the maximum to excitation of (xz, yz) degenerate in systems with two equivalent Cartesian axes x and y , and of (xy) to this hole in (x 2 - y 2 ) whereas species such as Cu(NHa)4(H20) +2 apparently presenting one, somewhat asymmetric band have all these transitions almost coinciding) it would be difficult to explain a factor higher than 2 as the intensity ratio between Cu(II) and Ni(II) with the same ligands.

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