Inorganic Chemistry Exam 2/3, 2011-05-05

ID# ________________________ Name ____________________________

1. (16 pts) Explain the following terms:

(a) Selection rules (coordination complex) (b) LMCT (c) MLCT
(d) Berry Puedorotation
2. (8 pts) Show the rate law for the following equation on the base of the
stationary-state approach for a dissociative reaction.
k1
L5MX L5M + X
k-1

k2
L5M + Y L5MY

3. (6 pts) Consider the half-lives of substitution reactions of the pairs of complexes:

Half-Lives Shorter than 1 Minute Half-Lives Longer than 1 Day
4-
[Cr(CN)6] [Cr(CN)6]3-
[Fe(H2O)6]3+ [Fe(CN)6]4-
Interpret the differences in half-lives in terms of the electronic structures.
4. (6 pts) Propose the interchange mechanism in square-planar (ML2TX) reactions of
(a) X direct substitution by Y; (b) solvent-assisted substitution
5. (10 pts) Write the ground terms (2S+1L) for the following electric configurations: (a)
d8 (Oh) (b) high spin d5 (Oh) (c) d4 (Td) (d) p3 (e) 4p13d1
6. (12 pts) Please describe all the six possible result of the dissociation mechanism and
stereochemical changes for trans-[M(en)2BX].
7. (8 pts) From the spectral data and Tanabe-Sugano diagrams, calculate o and B for
the complex, [V(H2O)6]3+, has absorption bands at 17,800 and 25,700 cm-1.
8. (10 pts) The compound trans-[Fe(o-phen)2(NCS)2] has a magnetic moment of 0.65
BM at 80K, increasing with temperature to 5.2 BM at 300K.
(a) Assuming a spin-only magnetic moment, calculate the numbers of unpaired
electrons at 80 and 300K.
(b) How can the increase in magnetic moment with temperature be explained?
9. (12 pts) Exchange of an H2O ligand on [Mn(CO)3(H2O)3]+ is much more rapid than
on the analogous [Re(CO)3(H2O)3]+. The change in volume on formation of the
activated complex is -4.50.4 cm3mol-1. The Mn complex has IR bands (C-O
stretching) at 3051 and 1944 cm-1. (a) Suggest why the Mn complex reacts more
rapidly than the Re complex. (b) On the basis of the IR spectrum, is the reactant
more likely a fac or mer isomer?

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10. (6 pts) What are the possible magnetic moment of Co(II) in tetrahedral, octahedral
11. (10 pts) The hydride complex, [ReH9]2-, has tricapped trigonal prismatic geometry.
Construct a representation using the hydrogen orbitals as a basis. Reduce this to
its component irreducible representations, and indicate which orbitals of Re are
suitable symmetry to interact with the hydrogen orbitals.

12. (9 pts) Compare the water-exchange rates in each set and explain what are the
major factor(s) in determining the rate of each aqueous complex.
(a) Be2+, Mg2+, Ca2+, Sr2+, Ba2+
(b) Zn2+, Cd2+, Hg2+
(c) V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+ (all M(H2O)62+)

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Supplementary materials