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Tutorial2 Peermarked Answers

The document provides model answers for peer-marked questions related to the electronic structure and bonding of d-block elements. It discusses the comparison of H2O and H2S in the spectrochemical series, highlighting the differences in their molecular orbitals and interactions with metals. Additionally, it classifies various ligands as σ only or π donor/acceptor based on their frontier orbitals and interactions with metal d orbitals.

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44 views3 pages

Tutorial2 Peermarked Answers

The document provides model answers for peer-marked questions related to the electronic structure and bonding of d-block elements. It discusses the comparison of H2O and H2S in the spectrochemical series, highlighting the differences in their molecular orbitals and interactions with metals. Additionally, it classifies various ligands as σ only or π donor/acceptor based on their frontier orbitals and interactions with metal d orbitals.

Uploaded by

2055945423
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as DOCX, PDF, TXT or read online on Scribd
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CHEM0014/15 - Electronic structure and bonding

of d-block elements – Peer-marked questions for


tutorial 2
Model Answers:
1. Discuss whether H2O or H2S is higher in the spectrochemical
series.
The comparison between H2O and H2S is the same as between NH3 and PH3.
H2O and H2S have similar MO diagrams, but S uses 3s and 3p AOs instead of the
2s and 2p of O.
Both H2O and H2S have two unshared electron pairs (we see in week 3 this
makes them pi donor ligands), one in the sp z level (a1 symmetry) and one in the
p AO perpendicular to the plane of the molecule (b2 symmetry).

Because both a1 and b2 levels are fully occupied, they are below the metal d
AOs in energy.
The strength of the interaction between S-M is higher than that of O-M for two
reasons:
1) S is less electronegative than O and the donor pairs are closer in energy to
the metal d levels, and
2) the S AOs are more diffuse and overlap better with the M-d AOs
Both effect enhance the splitting between d levels [2 marks]
2. Identify which of the following ligands can be classified as σ only,
and which as π donor/acceptor:

CO, BH3, H2S, Cl-, OH-, N2, NH3?


This question requires you to think about the frontier orbitals of the molecules
(you should be able to do this after the lectures on diatomic molecules in
CHEM0005 and the group theory section of CHEM0014) before we cover them in
week 3 lectures.
Only the MOs of the ligand closest in energy to the M-d AOs contribute
effectively; these are the donor pair(s) labelled as N - as seen in part 1 a
molecule can have more than one donor pair, and the pi/pi* levels if these are
present in the molecule.

E


LUMO 

HOMO N

CO
Look back at lectures in CHEM0005: the frontier MOs of CO are a sigma donor
pair on the C side, and there is a doubly degenerate, empty pi* level.
This makes CO a pi acceptor
N2
it is isostructural and isoelectronic to CO; it also has sigma donor pairs (one on
each N) and a doubly degenerate, empty pi* level.
Also a pi acceptor. The difference between CO and N 2 will be covered in week 3.
BH3
It only has sigma and sigma* MOs that are too low/too high in energy and are
not active in the interaction with M.
BH3 also has an empty valence MO, that makes BH 3 an acid molecule. As such it
is not a donor ligand; it could in special cases act as a sigma acceptor ligand
(labelled as Z) with electron rich metals that can donate electron pairs. We don't
consider this type of ligand explicitly in LFT - but you should be able to derive
the effect of Z ligands on the M-d levels by applying the rules discussed in the
lectures.
H2S
Discussed in question 1; it has two donor pairs, hence a pi donor
Cl-, OH-
In both cases, there are multiple donor pairs (4 in Cl - and 3 in OH-; represented
by the number of "double dots" in valence bond/VSEPR theory). Both are pi
donors
NH3
it has one unshared electron pair; all the other orbitals are of sigma/sigma* type,
hence there is only one active MO. Amines are sigma only ligands
1/2 mark for each molecule, plus 1/2 for the qualitative explanation (round to
next integer up)

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