2004. 6.16
P.S.先寫完close book交卷後才能再拿答案卷寫open book;只考130分鐘!!
Inorganic Chemistry
Total:188%
(part1,close book,102%)
1.Explain and/or make real exanples for the following terms. (16*3%=48%)
(a)solvolysis (b)gas-phase proton affinity
(c)ligand field stabilization energy (d)spectrochemical series
(e)linkage isomerism (f)Δ form of Co(ox)3 3+
(g)labile & inert transition metal ions
(h)inner-sphere electron transfer reaction
(i)Jahn Teller effect (j)π-acid
(k)Larporte & spin allowed transition (l)Orgel diagram of d2,d7 in Oh field
(m)chelate effect (n)EAN rule
(o)alkyne complex (p)The Cotton effect
2.The matalloporphyrin skeleton of heme is shown below.(題目有給圖) Answer
and explain the following questions.
(a)Complete the fully conjugate macrocycle by filling the double bonds at
the suitable positions. How many sp2 carbon atoms in this unit? (4%)
(b)Would you expect the high-spin or low-spin electronic configuration for
the iron center and the magnetic moment, if an Oh field is considered?
(4%)
(c)Extimate the Δ0 in cm^-1? (4%)
3.The rates of substitution for the following reaction depends on [py]
[Pt(dien)SCN]+ + py → [Pt(dien)py]2+ + SCN-
10^3 × kobsd 10^3 × [py]
6.6 1.24
8.2 2.48
25.0 12.4
(a)Draw the structures for the reactants and the products. (6%)
(b)Derive the rate law of this reaction and evaluate the rate constants.
(4%)
(c)Propose a mechanism to elaborate the data and the following table. (8%)
[Pt(dien)X]+ + py → [Pt(dien)py]2+ + X-
X- 10^6 × kobsd (s^-1)
H2O 1900
Cl- 35
I- 10
CN- 0.017
4.Urea ligands usually bond through the oxygen atom. 2-Pyridylmethylurea is
found to form the N,N㏑'-bonded square planar complex with Cu in
(N-N')CuMeCl, but N,O-bonded tetrahedral complex with Zn in (N=O)ZnMeCl.
//╲ H H
︳ ∥ N N
\\╱╲╱ ╲╱ ╲
N ∥
O
(a)Draw the structures for these two complexs and their possible
stereoisomers. (6%)
(b)Suggest a reason for such structural difference. (4%)
(c)How would you determine the structures, besides X-ray crystallography.
(8%)
5.According to Marcus' model, what energy contribution will be important to
the energy of activation of outer sphere electron transfer process? (6%)
(part2,open book,86%)
1.Explain and make real examples for the following terms. (6*4%=24%)
(a)fac- and mer- isomers (b)Dewar-Chatt-Dunkenson Model
(c)carbonylation reaction (d)β-hydride elimination
(e)Fisher carbene and Schrock carbene complexes
(f)Binap ligand
2.Consider the following reaction
Pt(PPh3)3 + MeI → trans-Pt(I)Me(PPh3)2 + PPh3
The rate of the reaction is governed by the following expression:
-d[Pt(PPh3)3] A[MeI][Pt(PPh3)3]
─────── = ─────────── (A,B=constants)
dt {[MeI] + B[Pt(PPh3)3]}
(a)Classify this reaction. (4%)
(b)Write a plausible mechanism for this reaction and show it agrees with the
rate law. (6%)
(c)Suggest an experiment that may confirm your proposed mechanism. Explain.
(6%)
3.Answer the following questions based on the data in Figure 13.6(課本圖附).
(a)Determine the rate law for this reaction and evaluate the rate constants.
(8%)
(b)Propose a plausible mechanism that can match with the data. (8%)
4.The following raection is found to proceed by an inner-sphere mechanism.
[Fe(CN)6]3- + [Co(CN5)]3- → [Fe(CN)6]4- + [Co(CN5)]2-
(a)Propose a plausible intermediate and how would you varify the mechanism?
(8%)
(b)Explain why there is no ligand transfer. (6%)
5.The CO de-insertion reaction below could either undergo migration of acetyl
CO or migration of the methyl group.
H3C O
╲ //
C CH3
|...CO -CO |...CO
OC─Mn─CO ──→ OC─Mn─CO
◢| ◢|
OC CO OC CO
(a)Explain how the pathway may be confirmed by isotope labeling with the
acetyl carbonyl carbon? (8%)
(b)Can the experiment be done by labeling other functional groups such as
the methyl group or the terminal carbonyls to achieve the same purpose?
Explain your results. (8%)
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