Advanced Tabulation of Coordination Complexes: Electronic Structure, Ligand Field Considerations,
Hybridization, Magnetic Behavior, and Notable Observations
Metal
Commentary on
Center
Ligand Electronic Magnetic Electronic Structure
Complex & d-
Classification Hybridization Property and Bonding
Electron
Dynamics
Count
High-spin
Paramagnetic octahedral
NCS⁻ (Weak sp³d² (outer
[Fe(NCS)₆]⁴⁻ Fe²⁺ (d⁶) (4 unpaired geometry due to
Field) orbital)
e⁻) weak field ligand
characteristics.
Paramagnetic Labile, exhibits
H₂O (Weak
[Ti(H₂O)₆]³⁺ Ti³⁺ (d¹) sp³d² (1 unpaired limited ligand field
Field)
e⁻) stabilization energy.
π-backbonding
CO (Strong d²sp³ (inner leads to effective
[V(CO)₆]⁻ V⁻ (d⁶) Diamagnetic
Field) orbital) pairing; low-spin,
18-electron system.
Neutral, low-spin,
CO (Strong demonstrates
[Cr(CO)₆] Cr⁰ (d⁶) d²sp³ Diamagnetic
Field) classical metal
carbonyl behavior.
Paramagnetic Typical high-spin
NH₃ (Weak
[Cr(NH₃)₆]³⁺ Cr³⁺ (d³) sp³d² (3 unpaired configuration for a
Field)
e⁻) d³ octahedral center.
Paramagnetic Outer orbital
F⁻ (Weak
[CrF₆]³⁺ Cr³⁺ (d³) sp³d² (3 unpaired complex, minimal
Field)
e⁻) CFSE.
Displays kinetic
Paramagnetic
H₂O (Weak lability, consistent
[Cr(H₂O)₆]³⁺ Cr³⁺ (d³) sp³d² (3 unpaired
Field) with aquo
e⁻)
complexes.
Mixed-ligand
Paramagnetic
NH₃, H₂O complex; indistinct
[Cr(NH₃)₃(H₂O)₃]³⁺ Cr³⁺ (d³) sp³d² (3 unpaired
(Weak Field) from [Cr(H₂O)₆]³⁺ in
e⁻)
electronic terms.
1
Metal
Commentary on
Center
Ligand Electronic Magnetic Electronic Structure
Complex & d-
Classification Hybridization Property and Bonding
Electron
Dynamics
Count
Strong-field ligand;
Paramagnetic
CN⁻ (Strong no pairing due to
[Cr(CN)₆]³⁻ Cr³⁺ (d³) d²sp³ (3 unpaired
Field) low d-electron
e⁻)
count.
Stabilized by
Paramagnetic
en (Strong chelation;
[Cr(en)₃]²⁺ Cr²⁺ (d⁴) d²sp³ (2 unpaired
Field) intermediate-spin
e⁻)
possibility.
Paramagnetic Exhibits octahedral
gly (Weak
[Cr(gly)₃] Cr³⁺ (d³) sp³d² (3 unpaired geometry; bidentate
Field)
e⁻) coordination.
Paramagnetic
Mn²⁺ H₂O (Weak High-spin d⁵ system;
[Mn(H₂O)₆]²⁺ sp³d² (5 unpaired
(d⁵) Field) highly labile.
e⁻)
Paramagnetic Analogous to aquo
Mn²⁺ NH₃ (Weak
[Mn(NH₃)₆]²⁺ sp³d² (5 unpaired complex; exhibits
(d⁵) Field)
e⁻) high-spin behavior.
Retains high-spin
Paramagnetic
Mn²⁻ NCS⁻ (Weak due to poor π-
[Mn(NCS)₆]⁴⁻ sp³d² (5 unpaired
(d⁵) Field) acceptor capacity of
e⁻)
NCS⁻.
Despite strong
Paramagnetic
Mn²⁺ en (Strong sp³d² or ligand field, no spin
[Mn(en)₃]²⁺ (5 unpaired
(d⁵) Field) d²sp³ pairing occurs (d⁵
e⁻)
stability).
Potential low-spin
Paramagnetic
Mn²⁺ CN⁻ (Strong d²sp³ behavior, spin-state
[Mn(CN)₆]²⁺ (3–5 unpaired
(d⁵) Field) (presumed) sensitive to
e⁻)
solvation effects.
Octahedral high-
Paramagnetic
NH₃ (Weak spin geometry; weak
[Fe(NH₃)₆]²⁺ Fe²⁺ (d⁶) sp³d² (4 unpaired
Field) field limits electron
e⁻)
pairing.
2
Metal
Commentary on
Center
Ligand Electronic Magnetic Electronic Structure
Complex & d-
Classification Hybridization Property and Bonding
Electron
Dynamics
Count
Exhibits complete
CN⁻ (Strong spin pairing;
[Fe(CN)₆]⁴⁻ Fe²⁻ (d⁶) d²sp³ Diamagnetic
Field) classical low-spin
hexacyanoferrate(II).
Pairing favored;
Paramagnetic
en (Strong electronic behavior
[Fe(en)₃]²⁺ Fe²⁺ (d⁶) d²sp³ (2 unpaired
Field) hinges on ligand
e⁻)
strength.
Mixed-ligand
Paramagnetic
complex; oxalate
[Fe(C₂O₄)₂(OH)₂]⁴⁻ Fe²⁻ (d⁶) C₂O₄²⁻, OH⁻ d²sp³ (approx. 4
promotes slight field
unpaired e⁻)
stabilization.
High-spin ferric
Paramagnetic
NH₃ (Weak complex; exhibits
[Fe(NH₃)₆]³⁺ Fe³⁺ (d⁵) sp³d² (5 unpaired
Field) typical octahedral
e⁻)
geometry.
Complete spin-
NH₃ (Weak pairing; low-spin
[Co(NH₃)₆]³⁺ Co³⁺ (d⁶) d²sp³ Diamagnetic
Field) due to relatively
strong NH₃ field.
Strong chelation +
en (Strong strong field = fully
[Co(en)₃]³⁺ Co³⁺ (d⁶) d²sp³ Diamagnetic
Field) paired, kinetically
inert.
