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Spin crossover is sometimes referred to as spin transition or spin equilibrium behavior. The change in spin state usually involves interchange of low spin (LS) and high spin (HS) configuration. [2] Spin crossover is commonly observed with first row transition metal complexes with a d 4 through d 7 electron configuration in an octahedral ligand ...
In octahedral complexes, the Jahn–Teller effect is most pronounced when an odd number of electrons occupy the e g orbitals. This situation arises in complexes with the configurations d 9, low-spin d 7 or high-spin d 4 complexes, all of which have doubly degenerate ground states.
In this case, Orgel diagrams are restricted to only high spin complexes. [8] Tanabe–Sugano diagrams do not have this restriction, and can be applied to situations when 10Dq is significantly greater than electron repulsion. Thus, Tanabe–Sugano diagrams are utilized in determining electron placements for high spin and low spin metal complexes.
Generally, the rates of ligand dissociation from low spin complexes are lower than dissociation rates from high spin complexes. In the case of octahedral complexes, electrons in the e g levels are anti-bonding with respect to the metal-ligand bonds. Famous "exchange inert" complexes are octahedral complexes of d 3 and low-spin d 6 metal ions ...
Due to a smaller crystal field splitting energy, the homoleptic halide complexes of the first transition series are all high spin. Only [CrCl 6] 3− is exchange inert. Homoleptic metal halide complexes are known with several stoichiometries, but the main ones are the hexahalometallates and the tetrahalometallates.
In an octahedral complex, the molecular orbitals created by coordination can be seen as resulting from the donation of two electrons by each of six σ-donor ligands to the d-orbitals on the metal. In octahedral complexes, ligands approach along the x -, y - and z -axes, so their σ-symmetry orbitals form bonding and anti-bonding combinations ...
An important class of complexes that violate the 18e rule are the 16-electron complexes with metal d 8 configurations. All high-spin d 8 metal ions are octahedral (or tetrahedral), but the low-spin d 8 metal ions are all square planar. Important examples of square-planar low-spin d 8 metal Ions are Rh(I), Ir(I), Ni(II), Pd(II), and Pt(II). At ...
Complementing the Laporte rule, is the spin-selection rule, which forbids transitions that involve changes in spin state. Violations of both the Laporte and spin-selection rules results in particularly low extinction coefficients. Illustrative of this combined effect is the faintness of even concentrated solutions of octahedral Mn(II) and Fe ...