課程名稱︰無機化學二 課程性質︰必修 課程教師︰彭旭明 開課學院：理學院 開課系所︰化學系 考試日期（年月日）︰2011/4/27 考試時限（分鐘）：120 是否需發放獎勵金：是 （如未明確表示，則不予發放） 試題 : 1.Werner won the nobel prize for chemistry in 1913. the citation os as follows:work on the linkage of atoms in molecules which has thrown new light on earlier investigations and opened up new fields of research especially in inorganic chemistry. Elasborate the statement and describe his coordination theory.(10%) 2.Give structures for the following (8%): (a) Bis(en)CoIII-m-hydroxobis(en)CoIII ion (b)DiaquadiiododinitritoPd(IV), all isomers (c)Fe(dtc)3, all isomers 3.Give the d orbitals splitting (qualitatively) in the following crystals fields(8%): (a)octahedral (b)tetrahedral (c)square planer (d)trigonal planar 4.Draw the molecular orbitals diagram of octahedral ML6 by considering sigma donor interaction only. Specify the deltaO(10%) Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3sigmah 6sigmad A1g1 1 1 1 1 1 1 1 1 1 A2g1 1 -1 -1 1 1 -1 1 1 -1 Eg 2 -1 0 0 2 2 0 -1 2 0 T1g3 0 -1 -1 1 3 1 0 -1 -1 T2g3 0 -1 -1 -1 3 -1 0 -1 1 A1u1 1 1 1 1 -1 -1 -1 -1 -1 A2u1 1 -1 -1 1 -1 1 -1 -1 1 Eu2 -1 0 0 2 -2 0 1 -2 0 T1u3 0 -1 1 -1 -3 -1 -1 0 1 T2u3 0 1 -1 -1 -3 1 0 1 -1 5.How does the pi-bonding effect on the deltao in octahedral ML6 complex? Give the spectrochemical series of ligands.(10%) 6.For eacg of the following configurations, construct a microstate table and reduce the table to its constituent free-ion terms. Ldentify the lowest energy term for each.(10%) (a)P3 (b)p1d1 (as in a 4p13d1 configuration) 7. {Co(NH3)6}2+ has absorption bands at 9000 and 21100 cm-1. Calcultare deltao and B for this ion.(Hints:The 4T1g>>>>>4A2g transition in this complex is too weak to be observed. The graph in Fiqure 1 may ne used for d7 as well as d2 complexes)(10%) E/B deltao/B V1 V2 V2/V1 0 0 15 - 10 8.74 21.5 2.46 20 18.2 31.4 1.73 30 27.9 40.8 1.46 40 37.7 50.4 1.34 50 47.6 60.2 1.26 8.An aqueous solution of Ni(NO3)2 is green. Addition of aqueous NJ3 causes the color of the solution to change to blue. If ethylenediamine is added to the green solution, the color changes to violet. Account for the colors of these complexes. Are they consistent with the explected positions of these ligands in the spectrochemical series?(6) 9.Match the following complex molecules with the proper ground state symbol: (a){Cr(NH3)6}3+ (b){CoF6}3+ (hign spin) (c){Mn(H2O)6}2+ (hign spin) (d){Ni(NH3)62+ (paramagnetic) (e){RhCl6}3- (diamagnetic) (f){Mn(CN)6}3- (low spin) (g){Ti(H2O)6}3+ (1)6A1g (2)1Aig (3)3Tig (4)4A2g (5)5T2g (6)3A2g (7)2T2g (7%) 10.A 2.00x1o^-4 M solution of Fe(S2CNEt2)3 (Et=C2H5) in CHCl3 at 25oC has absorption bands at 350nm (A=2.34), 514nm (A=0.532), 590nm (a=0.37), and 1540m, (A=0.0016).(6%) (a)Calcultate the molar absorptivity for this compound at each wavelength. (b)Are there bans more likely due to d-d transitions or charge-transfer transitions? Explain. 11. Predict whether there complexes would be labile or inert and explain your choices. THe magnetic moment is given in Bphr magnetons (mB) after each complex.(4%) (a)Ammonium oxopentachlorochromate(V) 1.82 (b)Potassium hexaiodomanganate(IV) 3.82 (c)Potassium hexacyanoferrate (III) 2.40 (d)Hexaammineiron(II) chloride 5.45 12.Consider the half-lives of substitution reactions of the pairs of complexes: Half-Lives Shorter than 1 minute Half-Lives Longer than 1 Day {Cr(CN)6}4- {Cr(CN)63- {Fe(H2O)63+ {Fe(CN)}64- {Co(H2O)6}2+ {Co(NH3)5(H2O)}3+ (H2O exchange) INterpret the difference in half-lives in terms of the electronic structure of eacg pair.(6%) 13.WHen the two isomers of Pt(NH3)2Cl2 react with thiourea {tu= S=C(NH2)2}, one product is {Pt(tu)4}2+ and the other is {Pt(NH3)2(tu)2}2+. Identify the initial isomers and explain the results.(4%) 14.Predict the products(quimolar mixtures of reactants)(3%): (a){Pt(CO)Cl3}- + NH3 >>>>> (b){Pt(NH3)Br3}- + NH3 >>>>> (c){(C2H4)PtCl3}- + NH3 >>>> 15.Exchange of an H2O ligand on {(CO)3Mn(H2O)3}+ is much more rapid than on the analogous {(CO)3Re(H2O)3}+. The activation volume (change in volume on formation of the activated complex) is -4.6+-0.4 cm^3. The Mn complex has infrared band at 2051 and 1944cm^-1 that can be attributed to C-O stretching vibrations.(6%) (a)Suggest why the Mn complex reacts more rapidly than the analogous Re complex. (b)Is the activation volume more consistent with an A (or Ia) or a D (or Id) mechanism? Explain. (c)On the basis of the IR spectrum, is the reactant more likely a fac or mer isomer? 16.Describe the following mechanisms and their evidences:(12%) (a)Sn1CB in base hydrolysis reaction. (b)Inner-sphere mechanism in electron transfer reaction. --

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