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3) Prefixes denote the number of each ligand type. Special prefixes and parentheses
are used if the ligand already contains a prefix.
2 di bis 6 hexa hexakis
3 tri tris 7 hepta heptakis
4 tetra tetrakis 8 octa octakis
5 penta pentakis 9 nona nonakis
10 deca decakis
a) dichlorobis(ethylenediamine)cobalt(III) fluoride [Co(en)2Cl2]F
b) tris(bipyridine)iron(II) chloride [Fe(bipy)3]Cl2
Fe3+ Co2+
3) Coordinate Covalent Bond = Ligand as Lewis Base and Metal as Lewis Acid
3) Problems with the theory
a) High energy 4d orbitals are unlikely participants in bonding
b) Doesn’t explain electronic spectra of transition metal complexes
B. Theory
1) Place degenerate set of 5 d-orbitals into an octahedral field of (-) charges (L:)
2) The electrons in the d-orbitals are repelled by the (-) charge of the ligands
3) The dz2 and dx2-y2 orbitals are most effected because their lobes point directly
along x,y,z axes where the point charges are
4) The dxy, dxz, and dyz orbitals aren’t destabilized as much
Octahedral Arrangement of d-Orbitals
5) The energy difference between these orbital sets is called “delta octahedral” = Do
a) The low energy set has t2g symmetry and are stabilized by –0.4 Do each
b) The high energy set has eg symmetry and are destabilized by +0.6 Do each
c) The total energy of the 5 d-orbitals is the same as in the uniform field = 0
(2)(+0.6 Do) + (3)(-0.4 Do) = 0
6) CFSE = Crystal Field Stabilization Energy = how much energy is gained
by the electrons in the 5 d-orbitals due to their splitting
a) Co(III) = d6 low spin
(6e-)(-0.4 Do) = -2.4 Do stabilization
b) Cu(II) = d9
(6e-)(-0.4 Do) + (3e-)(+0.6 Do) = -0.6 Do stabilization
c) Cu(I) = d10
(6e-)(-0.4 Do) + (4e-)(+0.6 Do) = 0 Do stabilization
MO Diagram for
an Octahedral Complex
7) All octahedral metal complexes will have the exact same MO diagram, only the
number of d-electrons will change
8) The 6 bonding MO’s, with lowered energy for their electron pairs is what holds
the metal complex together
2) Strong-Field Ligands = ligands whose orbitals interact strongly with metal ion
a) eg* is raised in energy
b) Do is large
3) Weak-Field Ligands = ligands whose orbitals interact weakly with metal ion
a) eg* is raised only slightly in energy
b) Do is small
4) Electron Spin
a) d0 – d3 and d8 – d10 octahedral complexes have only one possible
arrangement of electrons in the t2g and eg* MO’s
b) d4 – d7 octahedral complexes have two possible electronic arrangements
i. Low Spin = least number of unpaired electrons; favored by strong
field ligands with large Do
ii. High Spin = maximum number of unpaired electrons; favored by
weak field ligands with small Do
4) Splittings for other geometries:
Tetrahedral
Square Linear
Planar
E. The Spectrochemical Series
1) A list of Strong-Field through Weak-Field ligands
2) s-donors only
a) en > NH3 because it is more basic (stronger field ligand)
b) F- > Cl- > Br- > I- (basicity)
3) p-donors
a) Halides field strength is lowered due to p-donor ability
b) For similar reasons H2O, OH-, RCO2- also are weak field ligands
4) p-acceptors increase ligand field strength: CO, CN- > phen > NO2- >
NCS-
5) Combined Spectrochemical Series
CO, CN- > phen > NO2- > en > NH3 > NCS- > H2O > F- > RCO2- > OH- > Cl- > Br- > I-
Strong field, low spin s-donor only Weak field, high spin
p-acceptor p-donor
D. Electronic Spectra
1) A characteristic of transition metal complexes is color arising from
electronic transitions between d-orbitals of different energies
a) Electronic transition in an octahedral d1 complex