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1.

(30 pts) Define the following terms:


(a) Oxidative addition (b) Hydride elimination
(c) Hydroformylation (d) Hydrogenation
(e) Olefin Metathesis (f) Ring-opening metathesis polymerization
(a) (b)

(c) (d)

(e) (f)
2. (6 pts) MnCp2 is high spin, while MnCp*2 (Cp* = 5-C5Me5) is low spin. How many unpaired
electrons does each metal have, and which ligand has the stronger ligand field?

3. (14 pts) On the base of 18-electron rule, determine the unknown quantity or the first-row
transition metal for each of the following:
(a) [(5-C5H5)W(H)(CO)X] (b) [(CO)3Ni-Co(CO)3]Z (c) [(5-C5H5)Mn(CO)X]2 (Mn=Mn)
(d) M(CO)2(CS)(PPh3)Br] (e) [M(CO)7]+ (f) [(4-C4H4)(5-C5H5)M]+
(g) [(3-C3H5)(5-C5H5)M(CH3)(NO)] (linear M-N-O)
(a) 3 (b) 3- (c) 2 (d) Co (e) V (f) Ni (g) Cr
3. (6 pts) The 1H NMR spectrum of (C5H5)2Fe(CO)2 shows two peaks of equal area at room
temperature but has four resonances of relative intensity 5:2:2:1 at low temperatures. Explain.
At high temperature the C5H5 rings undergo rapid 1,2 shifts to give a single average proton
signal on the NMR time scale. At sufficiently low temperature, the different enviroments of the 1-
and 5- ring can be seen. The relative intensities are a =1, b=2, c=2, and d=5.
OC CO
b
d Fe a
d c
d
d d
b c

4. (10 pts) Analyzing the CO stretching vibrations for Ni(CO)4 and Cr(CO)6 with Td and Oh
symmetry.
Td, =4 1 0 0 2; Oh, =6 0 0 2 2 0 0 0 4 2
Td, =A1+T2, only T2 is IR active, 1 band; Oh, =A1g+Eg+T1u, only T1u is IR active, 1 band
5. (8 pts) Give the structural formulas from A to D:

A has strong IR bands at 1880 and 1830 cm-1; C has a 1H NMR spectrum consisting of two
singlets of relative intensity 1:5 at approximately -12 ppm and 5 ppm, respectively.

-
OC CO OC Br H
OC
Fe Fe Fe
CO CO
A B C D, benzene, C6H6

6. (8 pts) A Co(II) complex has absorption bands at 20,000 (4T1 4A2) and 16,000 (4T1 4T1) cm-1.
Calculate o and B for this complex.
o/B=10, B=800 cm-1, o=8000 cm-1
7. (9 pts) The d2 ions CrO44-, MnO43-, FeO42-, and RuO42- have been reported.
(a) Which of these has the largest value of t? The smallest? Explain briefly.
(b) Of the first three, which ion has the shortest metal-oxygen bond distance? Explain briefly.
(c) The charge-transfer transitions for the first three complexes occur at 43,000, 33,000, and
21,000 cm-1 respectively. Are these more likely to be ligand to metal or metal to ligand
charge-transfer transitions? Explain briefly.
(a) t: RuO42- > FeO42- > MnO43- > CrO44- t increases with the oxidation state of the metal; second
row greater than first row metals
(b) The nuclear charge of the ion is greatest in the isoelectronic series and exerts the strongest
attraction for the bonding electrons. FeO42- has the shortest metal-oxygen bond distance
(c) As the nuclear charge of the metal increases, the metal orbitals are pulled in to lower energies.
Consequently, less energy is needed to excite electrons from ligand orbitals to metal orbitals.
These are ligand to metal charge transfers.
8. (6 pts) Estimate the magnetic moments (spin-only) of the following species:
(a) [Fe(CN)6]3 (b) [Ni(H2O)6]2+ (c) [Cr(H2O)6]2+
(a) n=1, =1.7 BM (b) n=2, =2.8 BM (c) n=4, =4.9 BM
9. (8 pts) Assign absolute configurations ( or ) to the following:

(a) (b) (c) (d)

10. (10 pts) What is Jahn-Teller distortion? (3+4+3)


Jahn-Teller distortion describes the geometrical distortion of non-linear molecules under certain
situations. The effect is named after Hermann Arthur Jahn and Edward Teller, who first proposed it in
a theorem in 1937. The theorem essentially states that any non-linear molecule with a degenerate
electronic ground state will undergo a geometrical distortion that removes that degeneracy. This also
has the effect of lowering the overall energy of the complex.