Chem 312 - Chemtalk #4

Friday, February 17, 2012

1. Draw each of the complexes below as well as all possible isomers.

a) [IrCl(CO)Br(NH3)] - tetrahedral

chiral

b) [Cr(NH3)4(Cl2)]+

m
er as
co
eH w
o.
rs e
cis-chlorides trans-chlorides
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c) bis(ethylenediammine)dinitroferrate(III)
chiral
o
aC s
vi y re
ed d

cis-nitros cis-nitros trans-nitros

ar stu

non-superimpoasable
mirror image
d) tris(aquo)trichlorocobalt(III)
is
Th
sh

fac-chlorines mer-chlorines

Identify which of the isomers are chiral.

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 2. The d orbital electron configuration of octahedral complexes can either be described
as high-spin with the maximum possible number of unpaired d–electrons, or low–spin
containing one or more paired d–electrons. [Fe(H2O)6]2+ is a high–spin octahedral
complex. What is its spin–state (S=?)? Draw a d–orbital splitting diagram for this
complex and fill it with the appropriate number of electrons. Where does the final
electron go in this diagram? If you were to oxidize this molecule do you think this
would affect the bond lengths? Explain.
[Fe(H2O)62+ has 6 d-electrons. Since it is high-spin, it must
have a small Δ and the maximum number of unpaired
eg * electrons. The final electron goes in the lowest energy
level, pairing with another electron (highlighted in the
diagram). S = ½*4 = 2. The ground state electron
t2g configuration for a d5 molecule (the oxidized version)

m
er as
would still have two anti-bonding electrons in the eg*, so

co
bond lengths shouldn’t change.

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3. You have synthesized three compounds of chromium, but you accidentally

o.
rs e
forgot to label the vials after you isolated the solids. You know that you made
ou urc
Cr(NH3)63+, Cr(H2O)63+ and Cr(H2O)4Cl2+. You dissolve each solid in a separate
tube of water to get a purple solution, a yellow solution and a green solution.
Given the spectrochemical series:
o
aC s

CN- > NO2- > en > NH3 > H2O > OH- > F- > Cl- > Br- > I-
vi y re

Which solution is which?

Large Δ  small λ  absorbs blue

ed d
ar stu

Small Δ  large λ  absorbs red

NH3 > H2O > Cl-

is

Violet = Cr(H2O)63+
Th

Green = Cr(H2O)4Cl2+

Yellow = Cr(NH3)63+
sh

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