Bonding Approaches
Valence Bond theory provides the hybridization for octahedral complexes. For the first row transition metals, the hybridization can be: d2sp3 (using the 3d, 4s and 4p orbitals), or sp3d2 (using the 4s, 4p and 4d orbitals). The valence bond approach isnt used because it fails to explain the electronic spectra and magnetic moments of most complexes.
d Orbitals
d Orbital Splitting
__ __ e g dz2 dx2-y2 __ __ __ __ __
Spherical field
0.6o
__ dxy
0.4o
__ __ t 2g dxz dyz
Octahedral field
d Orbital Splitting
In some texts and articles, the gap in the d orbitals is assigned a value of 10Dq. The upper (eg) set goes up by 6Dq, and the lower set (t2g) goes down by 4Dq. The actual size of the gap varies with the metal and the ligands.
d Orbital Splitting
The colors exhibited by most transition metal complexes arises from the splitting of the d orbitals. As electrons transition from the lower t2g set to the eg set, light in the visible range is absorbed.
d Orbital Splitting
The splitting due to the nature of the ligand can be observed and measured using a spectrophotometer. Smaller values of o result in colors in the green range. Larger gaps shift the color to yellow.
Octahedral Symmetry
http://www.iumsc.indiana.edu/morphology/sym metry/octahedral.html
Magnetic Moments
A magnetic balance can be used to determine the magnetic moment of a substance. If a substance has unpaired electrons, it is paramagnetic, and attracted to a magnetic field. For the upper transition metals, the spinonly magnetic moment, s, can be used to determine the number of unpaired electrons. s = [n(n+2)]1/2
Magnetic Moments
The magnetic moment of a substance, in Bohr magnetons, can be related to the number of unpaired electrons in the compound. s = [n(n+2)]1/2 Where n is the number of unpaired electrons
Magnetic Moments
Complexes with 4-7 electrons in the d orbitals have two possibilities for the distribution of electrons. The complexes can be low spin, in which the electrons occupy the lower t2g set and pair up, or they can be high spin. In these complexes, the electrons will fill the upper eg set before pairing.
LFSE 0 .4o .8
1.2 .6
Considering Bonding
To obtain red for bonding, a set of cartesian coordinates is established for each of the ligands. The direction of the bonds is arbitrarily set as the y axis (or the py orbitals). The px and pz orbitals are used in bonding.
x x z z y y x y
z
y
z y y z
Considering Bonding
Consider only the px and pz orbitals on each of the ligands to obtain .
3C2 i 6S4 8S6 3h 6d 2 (=C4 ) -4 0 0 0 0 0
Considering Bonding
Oh E 8C3 6C2 6C4 12 0 0 0
This reduces to T1g + T2g + T1u + T2u. The T2g set has the same symmetry as the dxy, dyz and dxz orbitals on the metal. The T1u set has the same symmetry as the px, py and pz orbitals on the metal.
Considering Bonding
reduces to: T1g + T2g + T1u + T2u.
The T1g and T2u group orbitals for the ligands dont match the symmetry of any of the metal orbitals. The T1u set has the same symmetry as the px, py and pz orbitals on the metal. These orbitals are used primarily to make the bonds to the ligands. The T2g set has the same symmetry as the dxy, dyz and dxz orbitals on the metal.
Bonding
The main source of bonding is between the dxy, dyz and dxz orbitals on the metal and the d, p or * orbitals on the ligand.
Bonding
The ligand may have empty d or * orbitals and serve as a acceptor ligand, or full p or d orbitals and serve as a donor ligand.
Bonding
The empty antibonding orbital on CO can accept electron density from a filled d orbital on the metal. CO is a pi acceptor ligand. filled d orbital empty * orbital
Summary
1. All ligands are donors. In general, ligand that engage solely in bonding are in the middle of the spectrochemical series. Some very strong donors, such as CH3- and H- are found high in the series. 2. Ligands with filled p or d orbitals can also serve as donors. This results in a smaller value of o.
Summary
3. Ligands with empty p, d or * orbitals can also serve as acceptors. This results in a larger value of o. I-<Br-<Cl-<F-<H2O<NH3<PPh3<CO
donor< weak donor< only< acceptor
4 Coordinate Complexes
Square planar and tetrahedral complexes are quite common for certain transition metals. The splitting patterns of the d orbitals on the metal will differ depending on the geometry of the complex.
Tetrahedral Complexes
The dz2 and dx2-y2 orbitals point directly between the ligands in a tetrahedral arrangement. As a result, these two orbitals, designated as e in the point group Td, are lower in energy.
Tetrahedral Complexes
The t2 set of orbitals, consisting of the dxy, dyz, and dxz orbitals, are directed more in the direction of the ligands. These orbitals will be higher in energy in a tetrahedral field due to repulsion with the electrons on the ligands.
Tetrahedral Complexes
The size of the splitting, T, is considerable smaller than with comparable octahedral complexes. This is because only 4 bonds are formed, and the metal orbitals used in bonding dont point right at the ligands as they do in octahedral complexes.
Tetrahedral Complexes
In general, T 4/9 o. Since the splitting is smaller, all tetrahedral complexes are weakfield, high-spin cases.
Tetragonal Complexes
Six coordinate complexes, notably those of Cu2+, distort from octahedral geometry. One such distortion is called tetragonal distortion, in which the bonds along one axis elongate, with compression of the bond distances along the other two axes.
Tetragonal Complexes
The elongation along the z axis causes the d orbitals with density along the axis to drop in energy. As a result, the dxz and dyz orbitals lower in energy.
Tetragonal Complexes
The compression along the x and y axis causes orbitals with density along these axes to increase in energy. .
Tetragonal Complexes
For complexes with 1-3 electrons in the eg set of orbitals, this type of tetragonal distortion may lower the energy of the complex.
t2g
- w w s
w w -
w w -
1.2 .6