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Bridgeman 2007 Page 8

4 (iii) NH3 is higher in the Spectrochemical and Nephelauxetic Series than H2O.

Sketch the form of the electronic spectrum of [Ni(NH3)6]2+ showing how the
frequencies of the bands change with the respect to those in [Ni(H2O)6]2+.

For an octahedral d8 complex, there are three transitions (see page 7). Therefore,
[Ni(NH3)6]2+ also shows three bands in its spectrum.

The energy of the first transition is equal to oct. As NH3 is higher in the spectrochemical
series than H2O, the value of oct (NH3) > oct(H2O). The energy of the first band
therefore shifts to higher energy (higher wavenumber).

The first and second transitions differ only because of the effects of repulsion between the
d-electrons (see page 7):

(i) (t2g)6(eg)2 (t2g)5(eg)3 (low repulsion set)


(ii) (t2g)6(eg)2 (t2g)5(eg)3 (high repulsion set)

The size of the d-electron / d-electron repulsion is measured through the B parameter:
When this is large, the repulsion is large. This leads to a large splitting between
the first and second bands.
When this is small, the repulsion is small. This leads to a small splitting between
the first and second bands.

NH3 is higher in the Nephelauxetic series than H2O. Hence, there is a larger splitting in
the energies of the first and second bands.

Both [Ni(NH3)6]2+ and [Ni(H2O)6]2+ are octahedral so d-d bands in both are Laporte
forbidden and can only occur due to vibrations. Little difference in the intensity is
expected.

The red sketch below shows these salient features:


There are still 3 bands.
There is an overall shift to higher energy.
Bands 1 and 2 are further apart in energy.
The bands have similar intensity as before.

Visible spectrum of [Ni(OH2)6]2+ (black) and sketch of the spectrum of [Ni(NH3)6]2+ (red)
Bridgeman 2007 Page 8
The pictures below show the structures of the clusters [Re3Cl12]3-, Ru3(CO)12 and
Fe3(CO)12.

O O
Cl 3- C C
(OC) 4Ru Ru(CO)4
Cl3Re ReCl3
(OC)3Fe Fe(CO) 3
Cl Cl Ru
Re (CO)4
Cl 3 Fe
(CO)4
[Re3Cl12]3- Ru3(CO)12 Fe3(CO)12

4 (i) With the aid of orbital diagrams, describe the nature of the Ru-CO bond in Ru3(CO)12.

The HOMO of CO is the 2p orbital which is polarized towards C. CO uses this


orbital to -donate. It is a poor -donor (poor base) to non-transition metal
cations (including H+) and to transition metals with a d10 configuration. The -
donation is into an empty metal orbital of the correct orientation (such as dz2 and
dx2-y2 in an octahedral complex):

OC: M -donation

The LUMOs of CO are the pair of 2p* orbitals. These are again polarized
towards C. CO uses these orbitals to -accept electron density from a suitable
orientated d-orbital on a transition metal (such as dxz, dyz and dxy in an
octahedron. This mode of bonding involves M CO donation or -back
donation. It requires the presence of d-electrons on the metal and good overlap
between the metal and CO orbitals. The latter occurs only if the metal is in a low
( +2) oxidation. Higher oxidation states lead to the d-orbitals being too
contracted for overlap to be efficient. As the donation is into the * orbitals on
CO, it reduces the strength of the CO bond. This lengthens the CO bond and
reduces its stretching frequency. In principle, the -back donation could decrease
the CO bond order to two or less*.

M CO -back donation into the two * orbitals on CO

*
This weakening of the internal bonding of the ligand makes it more reactive: this is a common theme in complexes
involving -acceptor ligands and a strong reason for interest in this part of inorganic chemistry.
Bridgeman 2007 Page 8
In the absence of each other, both these modes of bonding are fairly weak
interactions as CO is intrinsically a poor -donor and poor -acceptor. However,
in both modes operate, they synergically enhance each other: the -donation leads
to a build up of electron density on the (electropositive) metal. The -back
donation acts to decrease this electron density so any -donation enhances the -
bonding. The -back bonding leads to an increase in electron density on the
(electropositive) carbon atom which in turn enhances its ability to -donate.

The result is a strong M-C bond with significant and -components. As the -
back donation weakens the CO bond, the final electron distribution is a
thermodynamic compromise between strengthening the M-C at the expense of the
CO bond.
Bridgeman 2007 Page 8