1) (8 marks) Classify each of the following ligands as L-type, X-type or Z-type:

(a) Cl- (b) aryl

(c) PPh3 (d) BR3

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er as
co
2) (8 marks) Classify each of the following ligands as -acceptor, -donor, or

eH w
only -donor.

o.
(a) Cl- rs e (b) H2O
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o
aC s
vi y re

(c) NH3 (d) CO

ed d
ar stu

3) (8 marks) Identify the metal oxidation state and dn configuration for each
of the following metal complexes:
sh is
Th

oxidation state dn configuration

(a) [Ni(H2O)6]2+ 2+ d8

(b) VCl3 3+ d2

(c) K4[Fe(CN)6)] 2+ d6

(d) (PPh3)3CoCl 1+ d8

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 4) (8 marks) The following complexes, [Ni(CN)4]2- and [NiCl4]2-, have the same
dn configuration, but different geometries.

(a) What is the geometry of [Ni(CN)4]2-?

square planar

(b) What is the geometry of [NiCl4]2-?

tetrahedral

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er as
(c) Provide a brief justification for the different geometries of these

co
complexes.

eH w
NC- is a -acceptor ligand; it is a strong field ligand. [Ni(CN)4]2- will

o.
rs e
preferentially form a square planar complex.
ou urc
Cl- is a -donor ligand; it is a weak field ligand. [NiCl4]2- will preferentially
form a tetrahedral complex.
o
aC s
vi y re
ed d
ar stu

5) (8 marks) Draw an orbital representation to depict the C=O π* orbital of

acetaldehyde.
sh is
Th

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 6) (8 marks) Predict the direction of the following equilibria in the gas phase
(i.e. Keq > 1, < 1 or = 1) and briefly explain your reasoning on the basis of
hard-soft acid base theory.

(a)

Keq < 1

Na+ is a hard acid; Cu+ is much softer (more polarizable)

F- is a hard base; Br- is much softer (more polarizable)

NaF is a better match than NaBr. CuBr is a better match than CuF.

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eH w
o.
rs e
ou urc
o

(b)
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Keq < 1

Ru2+ is a softer acid (more polarizable)than Fe2+

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ar stu

HS- is a softer base (more polarizable) than HO-

Ru(SH)2 is a better match than Ru(OH)2. Fe(OH)2 is a better match than

sh is

Fe(SH)2.
Th

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 7) (8 marks) Wilkinson’s catalyst, ClRh(PPh3)3, exhibits the following coupling
constants, J, in the 31P{1H} NMR spectrum: JRh,P = 189 Hz; JRh,P = 142 Hz;
JP,P = 38 Hz. The larger coupling constant is for the phosphine trans to
chloride.

(a) How many signals are present in the 31

P spectrum? Provide a brief
explanation.

There are two signals (two inequivalent phosphines, PA and PB)

(b) What is the multiplicity of each signal?

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co
PA: doublet of triplets

eH w
PB: doublet of doublets

o.
rs e
ou urc
o
aC s
vi y re

(c) Provide a Pascal tree diagram that is consistent with the expected
103
Rh{1H} NMR spectrum.
ed d
ar stu
sh is
Th

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 8) (12 marks) Predict the metal product of the following substitution reactions,
including stereochemistry where appropriate:

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eH w
o.
rs e
ou urc
o
aC s
vi y re
ed d
ar stu
sh is
Th

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 9) (8 marks) Provide a brief explanation for the difference in half-lives for
substitution reactions of the following complexes:

The Fe3+ complex has weak field ligands, whereas the Fe2+ complex has
strong field ligands.

A complex that is high spin will have low ligand field stabilisation energy
(LFSE). A complex that is low spin will have high ligand field stabilisation
energy (LFSE).

m
er as
The higher the LFSE, the more energy needed to reach the transition state.
Thus, a high spin complex is labile and a low spin complex is inert. A shorter

co
eH w
half-life is expected for a high spin complex.

o.
It is reasonable to say that the Fe3+ complex is high spin (labile) and the
rs e
Fe2+ complex is low spin (inert).
ou urc
o

10) (10 marks) The following self-exchange reaction proceeds with a rate
aC s

constant, k = 6.7 x 103 M-1 s-1:

vi y re
ed d
ar stu

(a) What is the expected mechanism of electron transfer? (You do not need
to draw any structures)
sh is

Outer sphere
Th

(b) Provide a brief explanation for your answer.

The complexes are low spin. The rate of electron transfer is thus faster than
the rate of ligand exchange. Also, an inner sphere mechanism requires a
bridging ligand: NH3 only has one lone pair and cannot bridge. Both of these
phenomena rule out an inner sphere mechanism.

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 11) (8 marks) Activation parameters are given for the reaction shown below.

(a) An intermediate is observed. Given this information, along with the

activation parameters, what mechanism of substitution does this data
support?

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co
eH w
o.
rs e
(b) Provide a brief justification for your answer in part (a).
ou urc
The large negative ΔS‡ means that the transition state is more ordered than
the reactants, consistent with an associative mechanism.
o
aC s

The small ΔH‡ means is consistent with more bond-making in the transition
vi y re

state than bond-breaking, and is thus also consistent with an associative

mechanism.
ed d

Because an intermediate is observed, the mechanism can definitively be

ar stu

stated as A.
sh is
Th

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 12) (6 marks) Provide a brief explanation for the trend in CO stretching
frequencies for the indicated transition metal complexes.

Complex 𝜐(CO) (cm-1)

[V(CO)6]- 1860

Cr(CO)6 2000

The vanadium complex is more electron rich than the chromium complex.
Thus, there is greater -backbonding in the vanadium complex, which weakens
the CO -bond (reduces the bond order), leading to the lower observed
frequency for the CO stretch.

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co
eH w
o.
rs e
ou urc
o
aC s
vi y re
ed d
ar stu
sh is
Th

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