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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 ...
Low-spin [Fe(NO 2) 6] 3− crystal field diagram. The Δ splitting of the d orbitals plays an important role in the electron spin state of a coordination complex. Three factors affect Δ: the period (row in periodic table) of the metal ion, the charge of the metal ion, and the field strength of the complex's ligands as described by the spectrochemical series.
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.
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 ...
As noted above, e g refers to the d z 2 and d x 2-y 2 which are higher in energy than the t 2g in octahedral complexes. If the energy required to pair two electrons is greater than Δ, the energy cost of placing an electron in an e g, high spin splitting occurs.
When a transition metal ion of configuration , = to , is in octahedral surroundings, its ground state may be low spin (LS) or high spin (HS), depending to a first approximation on the magnitude of the energy gap between and metal orbitals relative to the mean spin pairing energy (see Crystal field theory).
Ligand field scheme summarizing σ-bonding in the octahedral complex [Ti(H 2 O) 6] 3+.. According to Ligand Field Theory, the ns orbital is involved in bonding to the ligands and forms a strongly bonding orbital which has predominantly ligand character and the correspondingly strong anti-bonding orbital which is unfilled and usually well above the lowest unoccupied molecular orbital (LUMO).
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 ...