109年 - [無官方正解]109 國立成功大學碩士班_招生考試試題_化學系：無機化學#139158

1. Rank in order of increasing energy for the following spectroscopic techniques for inorganic chemistry:
A. EPR spectroscopy
B. Mössbauer spectroscopy
C. Infrared spectroscopy
D. UV-Vis (electronic) spectroscopy
E. X-ray absorption spectroscopy (XAS)(A)A ＜ B ＜ C ＜ D ＜ E(B)A ＜ C ＜ D ＜ E ＜ B(C)E ＜ D ＜ C ＜ B ＜ A(D)C ＜ A ＜ D ＜ B ＜ E

2. Determine the point group of triflate ion, F₃CSO₃-.(A)C_3h(B)C_2v(C)D_3d(D)C_3v
(E)D_3h

3. Determine the point group of O_s2Cl₈^2- (staggered).(A)D_4h(B)D_4d(C)C_4h(D)C_4v
(E)D₄

4. Which metal hydride, in each of the following pairs of compounds, should be more acidic?
(a) HV(CO)₆ or (b) HV(CO)₃(PPh₃)₃
(c) HRh(CO)(PPh₃)₂ or (d) HRh(CO)₂{P(OPh)₃}(A)(a) and (c)(B)(a) and (d)(C)(b) and (c)(D)(b) and (d)

5. For the compound that contains only one Fe environment, which Mössbauer spectrum would you NOT expect?(A)a singlet(B)a doublet(C)a triplet(D)a sextet

6. Which of the following acids is the strongest?(A)Fe(H₂O)₆³⁺(B)Fe(H₂O)₆²⁺(C)Co(H₂O)₆²⁺(D)Ni(H₂O)₆²⁺
(E)Zn(H₂O)₆²⁺

7. Pick the INCORRECT statement about early transition metals.(A)They are oxophilic.(B)They prefer lower oxidation states.(C)They are more electropositive than late transition metals.(D)Some of them are useful catalysts in olefin polymerization.
(E)They are usually classified as hard metals.

8. Determine the electron count for U in U(cot)₂ (cot = cyclooctatetraenyl dianion).(A)18(B)22(C)24(D)28
(E)32

9. Determine the electron count for Zr and Co in the following complex, respectively.
(A)10, 16(B)10, 18(C)18, 18(D)10, 10
(E)16, 10

10. What type of compounds or materials might exhibit the following behavior?
(A)paramagnetic(B)superparamagnetic(C)ferromagnetic(D)antiferromagnetic

11. What is NOT the typical behavior of a single molecule magnet (SMM)?(A)slow magnetization relaxation(B)magnetic hysteresis(C)long range ordering(D)typically consist of high-spin metal ions

12. What is the LUMO of O₂?(A)σ_u(B)π_g(C)σ_g(D)π_u
(E)δ_g

13. Below is the radial probability plot of the H atom, which one is most likely to be the 2p orbital?
(A)A(B)B(C)C(D)D

14. A crystal has the following cell parameters, what is the crystal system?
a ≠ b ≠ c, α = β = γ = 90°(A)cubic(B)orthorhombic(C)triclinic(D)monoclinic
(E)tetragonal

15. Which one of the following complexes has an effective magnetic moment (μeff) close to 5.9?(A)Fe(CN)₆^4-(B)Mn(H₂O)₆²⁺(C)Cu(H₂O)₆²⁺(D)Ni(H₂O)₆²⁺
(E)Co(H₂O)₆³⁺

16. What is NOT a vibration normal mode of ethylene?(A)a_g(B)b_2g(C)a_u(D)b_3u
(E)b_3g

17. What is the following symmetry type of the vibration normal mode?(A)e'(B)a1'(C)e"(D)a1"
(E)a2'

18. The following compound has an unusually long C-C bond length of 1.67 Å in the solid state, what is the main contributing force to the stability of this compound?
(A)hydrogen bond(B)dipole-dipole(C)dipole-induced dipole(D)dispersion
(E)ionic bond

19. One of the E_g SALCs for the octahedral complex is

What could be the other one?(A)(B)(C)(D)
(E)

20. What is the Mo-Mo bond order for Mo₂(CH₂Ph)₆?(A)1(B)2(C)3(D)4
(E)5

(a) First, construct the molecular orbital diagram of square pyramidal V(H₂O)₅⁴⁺. Assume that H₂O is a pure σ donor. Provide an appropriate label for each molecular orbital, sketch each molecular orbital, and fill in the correct number of electrons. (6%)

(b) Use the MO you created in (a), construct the MO diagram of octahedral VO(H₂O)₅²⁺ with V(H₂O)5⁴⁺ and O^2- ion. For simplicity, you can use the 3d orbitals for V. Provide an appropriate label for each molecular orbital, sketch each molecular orbital, and fill in the correct number of electrons. (7%)

(c) Based on your MO, what is the bond order between V and the O^2- ligand? (2%)

(a) Write down the symmetry labels for each of the Pd s, p, and d orbitals in the D_3h point group. (2%)

(b) Draw each SALC and give it a symmetry label. Assume that PPh₃ is a pure σ donor. Provide an appropriate label for each molecular orbital, sketch each molecular orbital, and fill in the correct number of electrons. (4%)

(c) Draw an MO diagram for Pd(PPh₃)₃. (6%)

(d) What is the bond order for Pd(PPh₃)₃? (2%)

(e) Is Pd(PPh₃)₃ paramagnetic or diamagnetic? (1%)

(a) Assign the formal oxidation state of Cu in this species. (2%)

(b) Experiment and computation showed that this species has a 4s⁰ 3d¹⁰ electronic configuration. Account for this observation by means of a simplified MO approach. (8%)

24. What is Tolman cone angle? Explain how it can influence the following equilibrium. How may this be important to catalysis? (10%)
Ni(PR₃)₄ ⇌ Ni(PR₃)₃ + PR₃

25. Why is X-ray crystallography not useful for the characterization of transition metal dihydrogen complex? Name at least two other methods that are useful and briefly elaborate. (10%)