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hexacyano- ion contains only one unpaired electron. Explain, using Crystal Field
Theory.
Answers
4) Indicate the type of isomerism exhibited by the following complexes and draw
structures for these isomers.
a. K[Cr(oxal)2(H2O)2].3H2O
b. [Co(en)3]Cl3
c. [CoCl(NO2)(NH3)4]Br
d. PtCl2(NH3)(H2O)
Answers
5) Give an example of each of the following:
a. Binuclear Complex
b. Metal Chelate
c. Low spin complex
d. High spin complex
e. Five coordinate complex.
6) a) Place the following ligands in increasing order in the Spectrochemical series:
CN-, NH3, Cl-,H2O
b) For octahedral first row transition metal complexes with between four and seven d
electrons, both high and low spin electron configurations are possible.
Use Crystal Field splitting diagrams to determine the number of unpaired electrons
and then calculate the expected spin-only magnetic moments.
7) a) Draw the complex, [Ni(en)3]2+, showing the optical isomers.
8) The complex ion [Ni(NH3)4]2+, forms on mixing aqueous solutions of ammonia and
a nickel salt.
a) If a solution contains 1.6 x 10-4 % of the nickel ions in the form of Ni2+ when the
concentration of free NH3 (aq) is 0.5M. What is the stability constant of the complex
[Ni(NH3)4]2+?
(Assume that this is the only complex present).
b) The octahedral ammine complex can be prepared by using a solution of ammonia
which has been supersaturated with ammonia gas, such that:
log K5 = 0.85
log K6 = 0.42.
Calculate the overall 6 for [Ni(NH3)6]2+.
Write the equations for the equilibria corresponding to K5 and K6.
Coordination Chemistry - CHEM1902 (C10K)
Answers to Tutorial Paper - 1
From the May 2004 Exam Paper.
1). (a) Give the Oxidation Number, d-orbital occupation, co-ordination number and
expected magnetic moment of the central metal ion in the following complexes.
Draw the expected structure.
(i) K3[Co(C2O4)3]
This octahedral Co(III) complex can display optical isomerism.
The CN = 6, the OS=3+, the d-orbital occupation is that of a LOW spin Co(III)
complex ie t2g6 eg0. All Co(III) are treated as LOW spin for CHEM1902 (C10K).
(ii) (NH4)2[CoF4]
This Co(II) complex is tetrahedral (for CHEM1902 (C10K) we have said that square
planar complexes will only be seen for d8 configurations and Co(II) is d7.
The d-orbital configuration is e4 t23 and the magnetic moment is 3.87 B.M { sqrt(15) }.
(iii) diamagnetic [NiCl2{P(C6H5)3}2]
The indication that the compound is diagmagnetic means it must be square planar
since a Ni(II) d8 configuration in a tetrahedral shape would be paramagnetic.
Examples with this formulation in BOTH tetrahedral and square planar shapes have
been found, generally the tetrahedral are green/blue while the square planar are red.
The triphenyl phosphine ligand is a neutral monodentate ligand.
(iv) cis-[CrCl2(bipy)2]Cl
Cr(III) has a d3 configuration (t2g3).
In this octahedral complex we do not need to worry about high/low spin since we
always fill from the lower level and there are 3 t 2g orbitals and 3 electrons and no
electrons left to occupy the eg level.
(v) [Mn(H2O)6]SO4
The aqua group gives rise to HIGH spin complexes so this octahedral Mn(II) d5
complex is paramagnetic with 5 unpaired electrons (t 2g3 eg2).
(b) Which of the complexes above can exhibit isomerism? Explain.
(i) can exhibit optical isomerism
(ii) does NOT show isomerism
(iii) the known square planar complexes with this formula are trans- and cis- forms
are theoretically possible.
(iv) The cis- form can exhibit optical isomerism and there is a possibility of
a trans- form as well.
(v) does NOT show isomerism.
(c) Give the IUPAC name for the complex (ii) in part (a).
ammonium tetrafluorocobaltate(II)
Note that the NH4+ cation is not coordinated and must be named before the anion.
2) Write down the systematic name for each of the following complexes and indicate
the oxidation state, electronic configuration, coordination number, stereochemistry
and magnetic moment of the central ion.
a) K[Cr(oxal)2(H2O)2] .3H2O
potassium diaquabis(oxalato)chromate(III) trihydrate
OS= 3, d3, t2g3eg0, CN=6, Shape =octahedral, 3 unpaired electrons.
b) CrCl3(pyr)3
trichloridotripyridinechromium(III)
OS= 3, d3, t2g3eg0, CN=6, Shape =octahedral, 3 unpaired electrons.
c) K4[Mn(CN)6]
potassium hexacyanidomanganate(II)
OS= 2, d5, t2g5eg0, CN=6, Shape =octahedral, 1 unpaired electron.
d) [CoCl(NH3)5] Cl2
pentaamminechloridocobalt(III) chloride
OS= 3, d6, t2g6eg0, CN=6, Shape =octahedral, 0 unpaired electrons. *
e) Cs[FeCl4]
caesium tetrachloridoferrate(III)
OS= 3, d5, e2t23, CN=4, Shape =tetrahedral**, 5 unpaired electrons.
f) [NiCl(en)2(NH3)]Cl
amminechlorobis(1,2-diaminoethane)nickel(II) chloride
OS= 2, d8, t2g6eg2, CN=6, Shape =octahedral, 2 unpaired electrons.
g) [Cu(NH3)4(H2O)]SO4
tetraammineaquacopper(II) sulfate
OS= 2, d9, splitting pattern not done for CHEM1902 , CN=5, Shape =square pyramid,
1 unpaired electron. (With 5 d-orbitals that can hold 10 electrons and Cu(II) with 9
electrons then it must mean there is 1 unpaired electron irrespective of the splitting
pattern of the energies of the d orbitals)
* for CHEM1902 (C10K), assume all Co(III) complexes are low-spin.
** for CHEM1902 (C10K), assume the only square planar complexes are for
d8 configurations
4) The hexaaquamanganese(II) ion contains five unpaired electrons, while the
hexacyano- ion contains only one unpaired electron. Explain, using Crystal Field
Theory.
Octahedral complexes with between 4 and 7 d electrons can give rise to either high or
low spin magnetic properties. Mn(II) has a d 5 configuration. In a weak octahedral
crystal field this splits to give t2g3eg2 but in a strong crystal field it gives t2g5eg0.
In the first case no pairing of electrons occurs, but in the second 2 pairs of electrons
are present leaving only one unpaired electron.
5) Indicate the type of isomerism exhibited by the following complexes and draw
structures for these isomers.
a) K [Cr(oxal)2(H2O)2] .3H2O
Both geometric (cis-, trans-) and optical isomers can exist.
b) [Co(en)3]Cl3
Two optical isomers can exist
c) [CoCl(NO2)(NH3)4]Br
Note that there are 10 possible isomers!
Hint: There are geometric, ionisation and linkage isomers possible.
d) PtCl2(NH3)(H2O)
Geometric (cis-, trans-) isomers can exist.
6)
Ans.
a)
b)
1.0 x 107.
1.9 x 108.
100
1.6 x 10 ^-4
(equation
Ni + NiL4
But since the amount of free Ni2+ is extremely small then the Total Ni(II) can be
approximated to NiL42+
The stability constant for the reaction forming the tetraammine is:
K
NiL4
--------Ni L^4
(equation 5.2)
Given that the NH3 concentration is 0.5M then equilibrium expression (equation 5.2)
can be simplified once it is recognised that the relationship in equation 5.1 is the
reciprocal of part of equation 5.2.
In other words the stability constant (K or 4) is
K
100
---------------------[1.6 x 10^-4] [0.5]^4
or 4 = 1.0 x 107
b) log 6 = log 4 + Log K5 + Log K6
Having just calculated 4 and given the last two stepwise stability constants then the
overall stability constant is:
log 6 = 7.0 + 0.85 + 0.42 = 8.27
or 6 = 1.9 x 108
6)
b)
K
[Nien3]
---------[Ni] [en]^3
(equation 6.1)
If at equilibrium [Ni(en)3]2+ is 0.08M and [en] is 0.40M then given that 3 is 4.07 x
1018
the concentration of free Ni2+ can be expressed as:
Ni
[Nien3]
---------K [en]^3
(equation 6.2)
Magnetic Moments
Lecture 4. CHEM1902 Coordination Chemistry
Magnetic moments are often used in conjunction with electronic spectra to gain
information about the oxidation number and stereochemistry of the central metal ion
in coordination complexes.
A common laboratory procedure for the determination of the magnetic moment for a
complex is the Gouy method which involves weighing a sample of the complex in the
presence and absence of a magnetic field and observing the difference in weight. A
template is provided for the calculations involved.
For first row transition metal ions in the free ion state, i.e. isolated ions in a vacuum,
all 5 of the 3d orbitals are degenerate.
A simple crystal field theory approach to the bonding in these ions assumes that when
they form octahedral complexes, the energy of the d orbitals are no longer degenerate
but are split such that two orbitals, the dx2-y2 and the dz2 (eg subset) are at higher energy
than the dxy, dxz, dyz orbitals (the t2g subset).
For octahedral ions with between 4 and 7 d electrons, this gives rise to 2 possible
arrangements called either high spin/weak field or low spin/strong field respectively.
The energy gap is dependent on the position of the coordinated ligands in the
SPECTROCHEMICAL SERIES.
See an interactive JAVA applet for examples.
Note: For CHEM1902 (C10K), we assume that all Co(III), d6 complexes are
octahedral and LOW spin, i.e. t2g6.
In tetrahedral complexes, the energy levels of the orbitals are again split, such that the
energy of two orbitals, the dx2-y2 and the dz2 (e subset) are now at lower energy (more
favoured) than the remaining three dxy, dxz, dyz (the t2 subset) which are destabilised.
Tetrahedral complexes are ALL high spin since the difference between the 2
subsets of energies of the orbitals is much smaller than is found in octahedral
complexes.
The usual relationship quoted between them is: tet 4/9 oct.
Square planar complexes are less commmon than tetrahedral and for CHEM1902 we
will assume that the only ions forming square planar complexes are d8 e.g. Ni(II),
Pd(II), Pt(II), etc. As with octahedral complexes, the energy gap between the dxy and
dx2-y2 is oct and these are considered strong field / low spin hence they are all
diamagnetic, =0 Bohr Magneton (B.M.)
The formula used to calculate the spin-only magnetic moment can be written in two
forms; the first based on the number of unpaired electrons, n, and the second based on
the electron spin quantum number, S. Since for each unpaired electron, n=1 and S=1/2
then the two formulae are clearly related and the answer obtained must be identical.
so= n(n+2) B.M.
so= 4S(S+1) B.M.
Comparison of calculated spin-only magnetic moments
with experimental data for some octahedral complexes
Ion
Config
1
Ti(III)
d (t2g )
3 = 1.73 1.6-1.7
V(III)
d2 (t2g2)
8 = 2.83 2.7-2.9
Cr(III)
d (t2g )
15 = 3.88 3.7-3.9
Cr(II)
Cr(II)
8 = 2.83 3.2-3.3
3 = 1.73 1.8-2.1
2
Fe(II)
Co(III)
Co(II)
Co(II)
3 = 1.73 1.8
Ni(II)
d (t2g eg )
8 = 2.83 2.9-3.3
Cu(II)
d9 (t2g6 eg3)
3 = 1.73 1.7-2.2
Config
d1 (e1)
so / B.M.
3 = 1.73
obs / B.M.
1.7-1.8
Cr(IV) / Mn(V)
d2 (e2)
Fe(V)
d3 (e2 t21)
4
8 = 2.83
2.6 - 2.8
15 = 3.88
3.6-3.7
d (e t2 )
24 = 4.90
Mn(II)
d5 (e2 t23)
Fe(II)
35 = 5.92
5.9-6.2
24 = 4.90
5.3-5.5
d (e t2 )
Co(II)
d (e t2 )
15 = 3.88
4.2-4.8
Ni(II)
d8 (e4 t24)
8 = 2.83
3.7-4.0
3 = 1.73
Cu(II)
d (e t2 )
Problem Set 10
1. Werner also studied the electrical conductance of aqueous solutions containing a
series of platinum(IV) complexes having the general formula Pt(NH 3)xCl4, where x is
an integer that varied from 2 to 6. His results can be summarized as:
Formula of Complex
Pt(NH3)6Cl4
Pt(NH3)5Cl4
Pt(NH3)4Cl4
Pt(NH3)3Cl4
Pt(NH3)2Cl4
Assuming that Pt(IV) forms octahedral complexes, (a) write the formulas for the five
compounds based on the dissociation results, (b) draw three-dimensional sketches of
the complexes, (include isomers that are possible), and (c) name each compound.
2. Crystal Field Theory fails in explaining why a neutral ligand such as CO can cause
a very large crystal field splitting. Use Molecular Orbital Theory to explain why the
CO ligand leads to a higher crystal field splitting.
3. In a linear field (as experienced, for example, by the d electrons in [Ag(NH 3)2]+),
how would Crystal Field Theory arrange the d orbitals according to increasing energy.
(Hint: Take z as the unique axis)
5. The octahedral structure is not the only possible six-possible coordinate structure.
One possibility is a planar hexagonal structure, with the metal occupying the central
position and with a ligand at each corner of the hexagon. Show that the existence of
two and only two isomers of [Co(NH3)4Cl2]+ provides evidence against the hexagonal
structure.
6. The equilibrium constants (formation constants) for two nickel complexes are
shown below:
[Ni(H2O)6]2+(aq) + 6NH3(aq) --> [Ni(NH3)6]2+(aq) + 6H2O(l) Kf = 4 x 108
[Ni(H2O)6]2+(aq) + 3en(aq) --> [Ni(en)3]2+(aq) + 6H2O(l) Kf = 2 x 1018
Although the donor atom is nitrogen in both instances, the formation constants are
very different. With (en), it is ten orders of magnitude bigger. The generally larger
formation constants for polydentate ligands is called the chelate effect. Explain this
effect using a concept you have seen earlier in this course.
7.
(a) Draw all the geometric isomers for an MA 2B4 complex.
(b) Draw all the geometric isomers for an MA 2B2 complex in a planar arrangement.
For a tetrahedral arrangement, are geometric isomers possible?
(c) Draw all the geometric isomers for an MA 3B3 complex.
(d) Draw all the geometric isomers for an MABCD complex in a planar arrangement.
Are optical isomers possible?
(e) Draw all the geometric isomers of [Cr(en)(NH 3)2BrCl]+. Which of these isomers
also has an optical isomer? Draw the various isomers.
8. The following reduction potentials are known for various 3+ first-row transition
metal ions in aqueous solution:
Mn3+(aq) + e- --> Mn2+(aq) Eo=1.51 V
Fe3+(aq) + e- --> Fe2+(aq) E0=0.77 V
Co3+(aq) + e- --> Co2+(aq) E0=1.84 V
Explain why the reduction potential for Fe3+ is abnormally low.
10. A Cu electrode is immersed in a solution that is 1.00 M in [Cu(NH 3)4]2+ and 1.00M
in NH3. When the cathode is a standard hydrogen electrode, the emf of the cell is
found to be 0.08 V. What is the formation constant for [Cu(NH 3)4]2+?
Pt(NH3)6Cl4
Pt(NH3)5Cl4
Pt(NH3)4Cl4
Pt(NH3)3Cl4
Pt(NH3)2Cl4
Assuming that Pt(IV) forms octahedral complexes, (a) write the formulas for the five
compounds based on the dissociation results, (b) draw three-dimensional sketches of
the complexes, (include isomers that are possible), and (c) name each compound.
(a)
Formula of Complex
Pt(NH3)6Cl4
[Pt(NH3)6]Cl4
Pt(NH3)5Cl4
[Pt(NH3)5Cl]Cl3
Pt(NH3)4Cl4
[Pt(NH3)4Cl2]Cl2
Pt(NH3)3Cl4
[Pt(NH3)3Cl3]Cl
Pt(NH3)2Cl4
[Pt(NH3)2Cl4]
diamminetetrachloroplatinum(IV)
2. Crystal Field Theory fails in explaining why a neutral ligand such as CO can cause
a very large crystal field splitting. Use Molecular Orbital Theory to explain why the
CO ligand leads to a higher crystal field splitting.
In Molecular Orbital Theory, the crystal field splitting is related to the difference
between the energy of the t2g and eg orbitals. The t2g orbitals are essentially
nonbonding and are composed of the dxz, dyz and dxy orbitals. The CO molecule
contains empty antibonding orbitals. These antibonding orbitals have the same
symmetry as the t2g orbitals and since they are empty, these additional overlap
(see figure below) will lead to a lowering in energy of the t 2g orbitals:
The t2g orbitals lower in energy but the eg orbitals (since they do not overlap with
the orbital) remain the same in energy, thus, leading to an increase in the
energy separation between the t2g and eg orbitals.
3. In a linear field (as experienced, for example, by the d electrons in [Ag(NH 3)2]+),
how would Crystal Field Theory arrange the d orbitals according to increasing energy.
(Hint: Take z as the unique axis)
With the two point charges along the +z and -z axis.
___ dz2
___ dxz ___ dyz
___ dxy ___ dx2-y2
5. The octahedral structure is not the only possible six-possible coordinate structure.
One possibility is a planar hexagonal structure, with the metal occupying the central
position and with a ligand at each corner of the hexagon. Show that the existence of
two and only two isomers of [Co(NH3)4Cl2]+ provides evidence against the hexagonal
structure.
6. The equilibrium constants (formation constants) for two nickel complexes are
shown below:
[Ni(H2O)6]2+(aq) + 6NH3(aq) --> [Ni(NH3)6]2+(aq) + 6H2O(l) Kf = 4 x 108
[Ni(H2O)6]2+(aq) + 3en(aq) --> [Ni(en)3]2+(aq) + 6H2O(l) Kf = 2 x 1018
Although the donor atom is nitrogen in both instances, the formation constants are
very different. With (en), it is ten orders of magnitude bigger. The generally larger
formation constants for polydentate ligands is called the chelate effect. Explain this
effect using a concept you have seen earlier in this course.
When a solvent is bound as a ligand to a transition metal ion, it loses a great
degree of freedom. The degree of randomness or entropy depends heavily on the
number of free molecules. When a chelating agent binds to a metal ion, it
liberates more than one ligand thereby increasing the number of free molecules
and, consequently, the entropy of the system.
7.
(b) Draw all the geometric isomers for an MA 2B2 complex in a planar arrangement.
For a tetrahedral arrangement, are geometric isomers possible?
(d) Draw all the geometric isomers for an MABCD complex in a planar arrangement.
Are optical isomers possible?
Optical isomers are not possible for square planar complexes because any planar
compound will have a mirror plane containing all the atoms and a disymmetric
molecule cannot have a mirror plane of symmetry.
(e) Draw all the geometric isomers of [Cr(en)(NH 3)2BrCl]+. Which of these isomers
also has an optical isomer? Draw the various isomers.
I, II, IIIa and IVa are geometric isomers; I and II have mirror planes, thus, they
do not have optical isomers. IIIa/IIIb and IVa/IVb are the pairs of optical
isomers.
8. The following reduction potentials are known for various 3+ first-row transition
metal ions in aqueous solution:
Mn3+(aq) + e- --> Mn2+(aq) Eo=1.51 V
Fe3+(aq) + e- --> Fe2+(aq) E0=0.77 V
Co3+(aq) + e- --> Co2+(aq) E0=1.84 V
Explain why the reduction potential for Fe3+ is abnormally low.
H2O is a weak-field ligand, thus, in all the hexaaqua octahedral species of the
above ions, the metal is in a high-spin state. Mn3+ is d4, Fe3+ is d5, Co3+ is d6. Only
Fe3+ has all its d orbitals half-filled which is a relatively stable electronic
configuration. Thus, the reduction potential of the Fe(III) ion is less than its
neighbors in the periodic table.
10. A Cu electrode is immersed in a solution that is 1.00 M in [Cu(NH 3)4]2+ and 1.00M
in NH3. When the cathode is a standard hydrogen electrode, the emf of the cell is
found to be 0.08 V. What is the formation constant for [Cu(NH 3)4]2+?
The process is:
(A) 2H+(aq) + Cu(s) + 4NH3(aq) --> H2(g) + [Cu(NH3)4]2+
E = E0 - RT/nF (ln Q)
Q = 1; E = E0 = 0.08 V
The above process (A) can be written as (I+II+III):
I. 2H+(aq) + 2e- --> H2(g)
II. Cu(s) --> Cu2+(aq) + 2eIII. Cu2+(aq) + 4NH3(aq) --> [Cu(NH3)4]2+(aq)
The reduction potentials relate to each other:
EA = EI + EII + EIII
EA is known from the experiment, 0.08 V.
EI is 0.00 V (hydrogen reference)
EII is -0.337 V (the negative of the standard reduction potential of Cu(II))
Thus, EIII should be 0.417 V.
E0 = (0.0592/2) log Kf
log Kf = 2 (0.417)/0.0592
Kf = 1.2 x 1014