Chem. 451 (Spring, 2003) Final Exam (100 pts)

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1 Chem. 451 (Spring, 2003) Final Exam (100 pts) Name: , SSN: , May 15, 2003 LAST, First Circle the alphabet segment of your Last Name: A-G H-L M-P Q-Z Please answer the following questions: Part I: Multiple Choices (21 pts: 3 pts). Please circle the ONE best answer: 1. Which of the following species does not obey the 18-e rule? a) (η 6 -C 6 H 6 ) 2 Mo b) [Ru(Cp)(CO) 2 ] 2 c) [IrCl(CO)(PPh 3 ) 2 ] d) [Rh(CO) 2 (µ-cl) 2 ] 2 2. The IR CO stretching frequencies in cm -1 for four carbonyl compounds were obtained and found to be 2040, 1890, 1736 and 1670 cm -1. The later value should result from a) [Mn(CO) 4 ] 3- b) Ni(CO) 4 c) [Fe(CO) 4 ] 2- d) [Co(CO) 4 ] - 3. What is the IUPAC name of the complex [Pt(en)(H 2 O)Cl 3 ]Cl a) Aquatrichloro(ethylenediamine)platinum(IV) chloride b) Aquatrichloro(ethylenediamine)platinate(IV) chloride c) Platinum(IV)aquatrichloro(ethylenediamin) chloride d) Aqua(ethylenediamine)trichloroplatinum(IV) chloride 4. What is the point group of trans-dichlorodiamineplatinum(ii)? a) D 4h b) Td c) C 2v d) C 2h 5. Consider the molecules: I) O=P(Cl) 3 II) NF 3 III) BF 3 IV) (η 4 -C 4 H 4 )Fe(CO) 3 (C 4 H 4 = cyclobutadiene). Which of these molecules belong to the point group C 3v? a) I, II and IV b) I and II c) I and IV d) II and III 6. Which of the following species is expected to exhibit a magnetic moment (µ due to spin only) of about 1.7 BM? a) [V(H 2 O) 6 ] 2+ b) [Fe(C 2 O 4 ) 3 ] 4- c) [CoCl 4 ] 2- d) [Fe(CN) 6 ] 3-1

2 7. Arrange the following complex ions in order of increasing oct (smallest oct = 1 & largest oct = 4): [Co(H 2 O) 6 ] 2+, [Co(NH 3 ) 6 ] 2+, [Co(NH 3 ) 6 ] 3+ and [Rh(NH 3 ) 6 ] 3+ a) [Co(H 2 O) 6 ] 2+ < [Co(NH 3 ) 6 ] 2+ < [Co(NH 3 ) 6 ] 3+ < [Rh(NH 3 ) 6 ] 3+ b) [Co(H 2 O) 6 ] 3+ < [Co(NH 3 ) 6 ] 3+ < [Co(NH 3 ) 6 ] 2+ < [Rh(NH 3 ) 6 ] 3+ c) [Co(H 2 O) 6 ] 2+ < [Co(NH 3 ) 6 ] 2+ < [Rh(NH 3 ) 6 ] 3+ < [Co(NH 3 ) 6 ] 3+ d) [Rh(NH 3 ) 6 ] 3+ < [Co(NH 3 ) 6 ] 3+ < [Co(NH 3 ) 6 ] 2+ < [Co(H 2 O) 6 ] 2+ Part II. (40 pts: 5 pts) Bonding in Coordination and Organometallic Compounds: 1. Name the following complexes, sketch all possible geometrical isomers and then indicate which of these complexes would exhibit optical activity and/or linkage isomerism? a) [CoBrCl(en)(NH 3 ) 2 ] + Name: b) [Co(NH 3 ) 5 (NO 2 )] 2+ Name 2

3 2. Describe the bonding (structure, splitting of d-orbitals and number of unpaired electrons) in each of the following complexes. a) Ni(CO) 4 b) Ru(NH 3 ) 6 ] 2+ c) trans-[co(en) 2 F 2 ] + d) Pt(NH 3 ) 2 Cl 2 e) [Mo 2 Cl 8 ] 4- f) CpCo(C 8 H 8 ) (C 8 H 8 = cyclooctatetraene) 3

4 Part III. (16 pts) Reaction Mechanisms and Organometallic Reactions: 1. (6 pts) Predict the products of the following reactions: a) Cr(CO) 6 + Na/Hg -THF b) Re(CO) 5 Br + [Mn(CO) 5 ] - 2. (5 pts) The following data have been reported for aquation at 25ºC of trans-[co(n 4 )LCl] 2+, where N 4 = cyclam (tetradentate chelate): trans-[co(n 4 )LCl] + + H 2 O trans-[co(n 4 )L(H 2 O)] 2+ + Cl - L - k (s -1 ) - NO x 10-5 Cl x 10-6 NCS x 10-9 CN x 10-7 a) What do these data suggest about the mechanism (dissociative or associative)? b) Write an equation for the rate-determining step of these reactions and briefly justify your answer? 3. (5 pts) The following activation parameters (at 30ºC in methanol) were measured for the reactions: [PtCl(L) 2 X] + py [PtCl(L) 2 py] + + X - Complex k 2 x 10 3 (M -1 s -1 ) S (J/mol.K) V (cm 3 /mol) trans-[pt(no 2 )(py) 2 Cl] cis-[pt(no 2 )(py) 2 Cl] trans-[pt(pet 3 ) 2 Cl 2 ] a) What mechanistic information can be extracted from these values (dissociative or associative)? c) Write an equation for the rate-determining step of these reactions and briefly justify your answer? 4

5 Part IV. (12 pts) Bioinorganic Chemistry: 1. What prevents simple iron porphyrins from functioning as O 2 carriers? 2. What features of successful models of Fe-porphyrin O 2 carriers have made it possible to avoid this problem (discuss with examples)? 5

6 3. It is remarkable that O 2 does not oxidize hemoglobin! Discuss the magnetic and structural changes of hemoglobin on going from the deoxy to the oxy form. Part V. (11 pts) Transition Metals: The following two graphs show the variation in ionization energies (IE) with atomic numbers: 1. The first two IEs of the first row of d-block elements increase only slightly with increasing atomic number, but the third IE increases strongly from Sc to Mn, then drops back at Fe, only to increase again to Zn. Explain these observations. 6

7 2. The first two IEs of the lanthanide elements increase only slightly with increasing atomic number, but the third IE increases strongly from La to Eu, then drops back at Gd, only to increase again to Yb and drop back at Lu. Explain these observations. 7

8 CHEM 451- Spring-2003 FINAL EXAM You will have 140 minutes to complete this exam. The exam has 7 pages plus Periodic Table When you are told to do so, tear off the Periodic Table cover sheet and use as required during exam H Li Na K Rb Cs Fr (223) 4 Be Mg Ca Sr Ba Ra Periodic Table of the Elements 21 Sc Y La Ac Ti Zr Hf Rf (261) 23 V Nb Ta Db (262) 24 Cr Mo W Sg (263) 25 Mn Tc (98) 75 Re Bh (262) 26 Fe Ru Os Hs (265) 27 Co Rh Ir Mt (266) 28 Ni Pd Pt Uun (269) 29 Cu Ag Au Uuu (272) 30 Zn Cd Hg Uub (277) 5 B Al Ga In Tl C Si Ge Sn Pb N P As Sb Bi O S Se Te Po (209) 9 F Cl Br I At (210) 2 He Ne Ar Kr Xe Rn (222) 58 Ce Th Pr Pa Nd U Pm (145) 93 Np Sm Pu (244) 63 Eu Am (243) 64 Gd Cm (247) 65 Tb Bk (247) 66 Dy Cf (251) 67 Ho Es (252) 68 Er Fm (257) 69 Tm Md (258) 70 Yb No (259) 71 Lu Lr (260) 8

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