2008학년도고급무기화학1 기말고사 (2008년 6월 10일 ) [2008 Advanced Inorganic Chemistry 1 Final Exam] mplex d n S Term LFSE ( o) Hours: 2:00PM-5:00 PM Answer the questions in the boxes given. Total Pages: 6 Total Problems: 9 1. 빈칸을채워라. 1. Fill the blanks. (5 x 4 =20) 이름 (omenclature) (a) [Cu(H 3) 4] 2+ (b) [PtCl 4] 2- [(CO) 4] - d 10 0 0 [Cr(C) 6] 4- [Fe(H 2O) 6] (hs) [(O 2) 6] 4- (hs) [(H 3) 6] (ls) MnO 4 - [Cu(H 2O) 6] 2+ 1 S 0 (c) Fe(S 2CMe 2) 3 배위구조그림 (Draw coordination structure) 4. (a) 문제 3의착물중에서 Jahn-Teller effect를보이는착물이 3개있다. 3개를골라라. 4. (a) Among the complexes of problem #3, three complexes show Jahn-Teller effect. Select the complexes. (2 x 3 =6) complexes (d) Diaquadiiododinitritopalladium(IV) (all ligand trans) (b) 위세착물이 Jahn-Teller effect를보이는이유를설명하여라. (b) Explain why the three complexes show Jahn-Teller effect. (15) 2. [ 2(trien) 3] + (trien= triethylenetetraamine) 에대한이성질체는다음이있다. 각각에대하여 absolute configuration (Δ 또는 Λ) 을결정하여라. 2. Followings are the stereo isomers of [ 2(trien) 3] + (trien= triethylenetetraamine). Determine the absolute configurations. (Δ or Λ) (2 x 4 = 8) (A) (B) (C) (D) absolute configuration (A) (B) (C) (D) 3. 다음착물들에대하여 d-전자배치 (d), 외톨이전자 (unpaired electron) 의수 (n), spin quantum number (S), ground-state molecular term symbol (Term), LFSE를써라. ( 전부 O h 배위구조로생각하고풀것 ) (Fig 1 참조 ) 3. What are the d-electron configuration (d), the number of unpaired electrons (n), spin quantum number (S), ground-state molecular term symbol (Term), and LFSE of the following complexes? (Assume all complexes have the O h coordination geometry.) (nsult Fig 1.) (1 x 30 = 30) - 1 -
5. Crystal field theory 에바탕하여 octahedral 구조에서의 d-오비탈갈라짐과 octahedral 구조에서 tetragonal elongation이일어날때의 d-오비탈갈라짐을그려라. 5. Based on the crystal field theory, draw d-orbital splittings in the octahedral field and the d-orbital splittings when the tetragonal elongation occurs from the octahedral structure. (10) 6. 자유 Cr 이온은 1s 2 2s 2 2p 6 3s 2 3p 6 3d 3 의전자배치를한다. 착이온 Cr(H 3) x 에대하여다음에답하라. (H 3 는 σ-donor ligand 이다.) 6. Free Cr ion has the electron configuration of 1s 2 2s 2 2p 6 3s 2 3p 6 3d 3. Answer the following questions about Cr(H 3) x. (H 3 is a σ-donor ligand.) (b) 각겹침모델 (angular overlap model) 을이용하여 Cr 의 d-orbital 과 H 3 의 σ-donor orbital의에너지준위가사면체구조인 Cr(H 3) 4 착물을이룰때어떻게변화하는지를에너지준위도를그리고상대적인에너지준위를 e σ 로표시하여라. ( 구하는과정도쓸것. Table 1 참조 ) (a) Draw the energy level diagram of the d-orbitals of Cr and the σ -donor orbitals of H 3 in tetrahedral Cr(H 3) 6 complex, based on angular overlap model. Energy levels should be noted in e σ unit. (Write the process to get the energy level diagram. nsult Table 1.) (15) (a) 각겹침모델 (angular overlap model) 을이용하여 Cr 의 d-orbital 과 H 3 의 σ-donor orbital의에너지준위가팔면체구조인 Cr(H 3) 6 착물을이룰때어떻게변화하는지를에너지준위도를그리고상대적인에너지준위를 e σ 로표시하여라. ( 구하는과정도쓸것. Table 1 참조 ) (a) Draw the energy level diagram of the d-orbitals of Cr and the σ -donor orbitals of H 3 in octahedral Cr(H 3) 6 complex, based on angular overlap model. Energy levels should be noted in e σ unit. (Write the process to get the energy level diagram. nsult Table 1.) (15) - 2 -
(c) (a) 와 (b) 로부터 Δ t/δ o 값은얼마인지계산하라. (Δ o = octahedral orbital splitting parameter, Δ t = tetrahedral orbital splitting parameter) (c) From the results of (a) and (b), calculate the value of Δ t/δ o. (Δ o = octahedral orbital splitting parameter, Δ t = tetrahedral orbital splitting parameter) (5) (d) Table 2를참조하여 Cr(H 3) 6 에서 Δ o 는얼마가되는지 cm -1 단위로계산하여라. (d) In octahedral Cr(H 3) 6, calculate Δ o in cm -1 unit. (nsult Table 2.) (5) M ML 6 L 6 (e) Table 2를참조하여 Cr(H 3) 4 에서 Δ t 는얼마가되는지 cm -1 단위로계산하여라. (Table 2는팔면체구조에대한것이지만그대로적용하여라.) (e) In tetrahedral Cr(H 3) 6, calculate Δ o in cm -1 unit. (Though Table 2 is for octahedral complexes, use the table for this question.) (5) 다음에주어진 symmetry adapted orbital 그림위에모든 MO들의그림을그려라. 만일 non-bonding orbital이있다면빈네모에그려라. Draw the all MOs on the given symmetry adapted orbitals. If there is(are) non-bonding MO(s), draw the non-bonding tobital(s) in the empty box.) (f) Crystal Field Theory 에의한 Crystal Field Stabilization Energy (= Ligand Field Stabilization Energy) 가 Cr(H 3) 6 와 Cr(H 3) 4 에대하여각각얼마인지 cm -1 단위로답하라. (f) What are the Crystal Field Stabilization Energy (= Ligand Field Stabilization Energy) of the octahedral Cr(H 3) 6 and the tetrahedral Cr(H 3) 4, respectively, in cm -1 unit? (10) (g) (f) 의결과로보아 Cr 와 H 3 가배위결합할때선호하는것은팔면 체 Cr(H 3) 6 이겠는가사면체 Cr(H 3) 4 이겠는가? (g) When Cr and H 3 form a coordination complex, will it be an octahedral Cr(H 3) 6 or a tetrahedral Cr(H 3) 4 )? Predict the answer, based on the answer of (f). (5) 7. [Fe(H 2O) 6] 와같이 octahedral 구조를가지는착물의 MO의에너지준위그림은다음과같다. 7. Following is the energy level diagram of MOs of an octahedral complex like [Fe(H 2O) 6] 3. (2 x 15 =30) - 3 -
9. i 2+ 착물에대한다음의데이터가있다. (Fig 1 참조 ) 9. Following data are obtained from the experiments of i 2+ complexes. (nsult Fig 1.) 착물 (mplexes) 흡수선 (Absorption bands) (cm -1 ) A B C [i(h 2O) 6] 2+ 8,500 15,400 26,000 [i(h 3) 6] 2+ 10,750 17,500 28,200 [i(os(ch 3) 2) 6] 2+ 7,728 12,970 24,038 [i(dma) 6] 2+ 7,576 12,738 23,809 (a) 흡수선 A, B, C는각각어느상태에서어느상태로의전이에해당하는가? (a) Which transitions do the absorption bands, A, B, and C correspond to, respectively? (5 x 3 = 15) Ground state term symbol -> Excited state term symbol A B C (b) 팔면체 i 2+ 착물에대하여 o 값은 ground state 와 first excited state 사이의에너지차이에해당한다. 각착물에대하여 o 값이어떻게되는지적어라. (b) For the octahedral i 2+ complexes, o corresponds to the energy difference between the ground state and the first excited state. What are the o of each complex? (2 x 4 = 8) [i(h 2O) 6] 2+ cm -1 [i(h 3) 6] 2+ cm -1 [i(os(ch 3) 2) 6] 2+ cm -1 [i(dma) 6] 2+ cm -1 (c) (b) 의결과를바탕으로위 i 2+ 착물에있는리간드들사이의 spectrochemical series 의순서를써라. (c) Based on the answers of (b), write the spectrochemical series of the ligands in the above i 2+ complexes. (10) 8. [VF 6] 3- 는 14800 cm -1 와 23250 cm -1 에서두개의흡수선을갖는다. ( 세번째흡수선은자외선영역 ) Fig 1 의여러 Tanabe-Sugano diagram 중에서해당하는 diagram을찾아 diagram 위에두흡수선이어느상태에서어느상태로의전이에해당하는지화살표로표시하여라. 8. [VF 6] 3- has the electronic absorption bands at 14800 cm -1 and 23250 cm -1. (The third absorption band is in ultraviolet range.) Select the appropriate Tanabe-Sugano diagram for [VF 6] 3- in Fig 1 and mark arrows the corresponding transitions to the above two bands on the diagram in Fig 1. (10) - 4 -
Fig 1. Simplified Tanabe-Sugano diagrams for d 2 -d 8 electron configuration - 5 -
Table 1. Angular Overlap Parameters: Sigma interactions Table 2. Angular Overlap Parameters - 6 -