Homework 4 Answerkey PDF

Homework #4: Chem 208 ANSWER KEY (50 pts total)
Q. 1-8 Consider the complexes below. For each, give the metal oxidation state and d-electron count. Next,
draw the crystal field diagram and fill in the electrons appropriately, considering whether the complex is
high spin or low spin (if applicable). Using the diagram you drew, state whether the complex is paramagnetic
(has unpaired electrons) or diamagnetic (does not have unpaired electrons).
Au(III), d8 Mn(III), d4 Mn(I), d6 Co(III), d6
___ ___ ___ ___
_|_ _|_ ___

_||_
_||_ _|_ _|_ _|_ _|_

_||_ _||_ _||_ _||_ _||_ _||_ _||_
Diamagnetic paramagnetic (high spin b/c Td) (low spin) diamagnetic (low spin) paramagnetic
Q. 9-11 Predict whether the following complexes are expected to experience a Jahn-Teller distortion. 2 pts
each, 6 pts total.
Ir(II), d7 octahedral Cr(II), d4 octahedral Mn(II), d5 octahedral
(low spin b/c 3rd row M) (high spin b/c low ox. st.) (high spin b/c low ox. st. and weak ligs)
Yes, this will have JT distortion Yes, this will have JT distortion No, this will not have JT distortion
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Q. 12 Which of the following complex ions is tetrahedral?
[NiCl4]2–
Q. 13 Match up the correct formula and magnetic property. Which pair is correct?
[Co(NH3)6]3+; diamagnetic
Q. 14 [Cr(CN)6]3– is expected to be:
paramagnetic with μeff = 3.87 μB
Q. 15 For which pair of complexes is the order of values of Δoct correct?
[Rh(NH3)6]3+ > [Co(NH3)6]3+
Q. 16 The CFSE for a high-spin d4 octahedral complex is:
–0.6Δoct
Q. 17 Which statement is correct?
Tetrahedral complexes of first row metal ions are almost always high-spin.
Q. 18 The octahedral CFSE for a low-spin d5 ion is: –2.0Δoct + xP where the value of x is:
Use for Q. 19 – 23 The ruthenium porphyrin complex I below can be sequentially oxidized using N2O
(releasing N2) to afford the oxo complexes II and III, respectively.
Q. 19 How would you classify the porphyrin ligand using L and X-type notation? 1 pt L2X2
Q. 20- 22 Give the Ru oxidation state and d-electron count for complexes I, II, and III: 3 pts total
Complex I: Ru(II), d6
Complex II: Ru(IV), d4
Complex III: Ru(VI), d2
Q. 23 Draw the appropriate crystal field splitting diagram for I and show how introduction of the oxo groups
causes the crystal field diagrams to change for II and III. Consider that the Ru=O bonds are shorter than the
Ru-N bonds and take the z-axis to be the axis along which the oxo ligands are introduced. 10 pts total
Make sure you have: clearly labeled each diagram as corresponding to complexes I, II, or III; labeled the d
orbitals on each diagram; drawn the correct relative ordering of d orbitals as predicted by crystal field
theory; included the correct number of electrons in each diagram.
Use for Q. 24-28: Complexes with metal-metal multiple bonds are some of the most
unique and interesting complexes in inorganic chemistry. They were studied
extensively by Albert Cotton and co-workers in the early 1960’s. One of the simplest
examples of such a complex is [Re2Cl8]2- (image at right).
Q. 24 We can think of [Re2Cl8]2- as being composed of two [ReCl4]- fragments. Give

the oxidation state and d-electron count of Re in this fragment. (1 pt) Re(III), d4
Q. 25 What is the point group of the [ReCl4]- fragments? (1 pt) D4h
Q. 26 a) Using your knowledge of crystal field theory and the appropriate character table, draw an orbital
splitting diagram for the [ReCl4]- fragment. Label each d orbital in your splitting diagram with both its name
(i.e., dxy, etc.) and its Mullikan symbol (i.e., a1g). Consider the z-axis as the axis along which the Re-Re bond
will be eventually formed.
b) Draw a MO diagram for [Re2Cl8]2- by bringing together two [ReCl4]- fragments (this is just a more
complicated version of how we drew homodiatomic MO diagrams by bringing together sets of atomic
orbitals on each bonding partner). Label the resulting MO’s with their appropriate Mullikan symbols, denote
whether they are bonding/antibonding/non-bonding, and designate whether they result from σ, π, or δ
interactions. Make sure you fill your MO diagram with the correct number of electrons. (c and d together: 10
pts total).
Note: You didn’t need to include Mullikan symbols of the final MO’s; this is complicated since the final
complex is a different point group than the fragments.
Q. 27 What is the Re-Re bond order, according to your diagram? 1 pt 4
Q. 28 According to your diagram, provide two ways to reduce the Re-Re bond order by 1. (2 pts) You could
reduce by 2 electrons (fill delta*) or oxidize by 2 electrons (empty delta)
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Homework #4: Chem 208 ANSWER KEY (50 pts total)

Au(III), d8 Mn(III), d4 Mn(I), d6 Co(III), d6

_ _ _ _

_|_ _|_ ___

_||_ _|_ _|_ _|_ _|_

Ir(II), d7 octahedral Cr(II), d4 octahedral Mn(II), d5 octahedral

Q. 14 [Cr(CN)6]3– is expected to be:

paramagnetic with μeff = 3.87 μB

Q. 15 For which pair of complexes is the order of values of Δoct correct?

[Rh(NH3)6]3+ > [Co(NH3)6]3+

Q. 16 The CFSE for a high-spin d4 octahedral complex is:

Q. 17 Which statement is correct?

Q. 24 We can think of [Re2Cl8]2- as being composed of two [ReCl4]- fragments. Give

Q. 25 What is the point group of the [ReCl4]- fragments? (1 pt) D4h

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