THE UNIVERSITY OF THE WEST INDIES DEPARTMENT OF BIOLOGICAL AND CHEMICAL SCIENCES (CHEM3100 - INORGANIC CHEMISTRY I INCOURSE TEST #1 Wednesday 7 November 2018 Time allowed: 50 minutes. Attempt all questions. The test is worth 35 marks. Non-programmable calculators are allowed. NAME Answer Sieet 4. The “NMR spectrum of CIF shows a [2 marks] Doublet and triplet for a T-shaped structure Singlet for a trigonal planar structure . Singlet for a trigonal pyramidal structure d. Doublet and singlet for a T-shaped structure 2. ‘Which list below gives only spin active nuclei? ex 190, 18 B. 1H, H, "°C c. 7H, 2, °F d. 1H, °C, 8F [1 mark] Br How many peaks do you expect to see in the 'H NMR spectra of (CHs)2CHBr and CHsCH2CH2Br, respectively? [1 mark] 3,2 . 2, 2, ose @2 4. Chemical shifts originate from: won [1 mark] a_magnetic momentum lectron shielding ©. free induction decay d. scalar coupling (J-coupling) 5. __ Integration of H signal intensities (or peak area) gives information about [1 mark] the absolute number of protons corresponding to the resonance frequencies he ratio of the number of protons corresponding to the resonance frequencies . the types of protons corresponding to the resonance frequencies d. intensities of protons relative to the solvent peaksThe bromine pentafluoride molecule is square pyramidal (Cay symmetry) with an axial bond length of 168 pm and the equatorial bonds being 178 pm in length. Its 1°F NMR spectrum shows two peaks at +132 ppm and +269 ppm, relative to CCIF. Showing all working: a. Draw the structure of bromine pentafluoride [1 mark] te Faw Ser i ee SNe b, What are the relative intensities (integrations) ofthe two peaks? [2 marks} Vand oy ©. What are the shapes of the peaks? 1 . rks] Fan FL coupling Ficfa copy Ante AanL+l 2WQ)H = S Dquhter 2C)G)H = 2 DS doweter a o ; Fae geo , Fo- Mer conplucg aarH sea Hey qunat ROC) +1 4 Dquacte aes 7 one : Fo- Ter comply Fa- Br coupling Antu Ant ROU) Ma Set 20CI4A) H F429 ett tels of quartelt qusnter of quartets of-quastelt doutterof questels ef d. Would you expect the peaks in a “*F NMR spectrum of [Fs to be observed at more downfield or more upfield chemical shifts than those in the bromine pentafluoride spectrum? Give a brief reason for your answer. [3 marks] Upfretd FS Uts cterckronegstive Uae Br , F pata mow electron denitty devo tel? ". sheldecl7. Predict the "°F NMR spectra of PFs at room temperature and at 80 K. Show all ‘working. Baan Boon Tempe our | P se SF sé 2 lee Sep “™ S bp olp degoral bipyramdal At oom tempat dir to pruuderstahon, ae axad ond equated bends nterchange dispose aU die frcitico ate Ate Sane. Vdupe ef F *. 1 peak Ee _ St p coupling anI +l 2CE)HI =a > dole [12% marks] 2 - a 7 | a oF JL <—— ppmFe bo SS ar m—P m 2 types e{ F +, 2 peoko a FL complrna anit 7 AGA H = 2 | dryta Fatal anL +l 2QYG)+! =a =D dovthar clecplek of Perera eee Bl deapteks Fo- Fa couptts AnL+! Aca) Fl =H = quad R-e aQnL+l 2a)c4) +1 =a > seen P aij dacietahy ered aeatie| iquevtele es8. The "°F NMR spectrum of the anion [CFsCF2"'BFsJ- is shown in the figure below (top spectrum). The structure, chemical shifts and coupling constants are as follows: 1360 5 153.6 S/ppn Account for the appearance of the top spectrum, Bdiunes of F 2 p feak ab ~ 73-20 oe — Pre. Fa FL coup anrL+t 2D U4) +1 = 3 Drplet [8% marks] RF couply an +t 2Ca)CK) +1 = 4S quartet + _ Trak 7 “Taek, Guateh of deiptateRoot at -126-01 pp FLFR comply Ani+t 2D C+ = 4 = quote Fam Fe camping Qni+t aca Cyr D4 =D quortet Fe "B conplds Qnt +1 20%) Hay SS quecsee ' 2. Mere 7 TR 7a Guowteb | quostets 4 quactels Peak ob —153-44 por RM Fa couptuts anit acc’) H=Y4 => quartet Fo- Fy couplity AnLH C24) H = 3 Stepper QO)CK) +1 = HD quartet i Law 3. ng 7 OMe 7 Guartet of quartets +} dacplats“Lanthanide series. tActinide: series a TA 8A 1 ve 7 1] 2 H | 2A Current American usage 3A 4A 5A 6A! H | He ong| 2 -—————— 1UPAC notation 1314 15 16 | 00/4009 ala @]7)8|s]w Ui | Be c|N/0|F|Ne esa 9012 2031 | 12.01 | 1.01 | 16.00 | 9.00 | 20.18 44 | 12 wap fis [16 [17 [8 Na}Mg|38 48 5B 6B 7B=———e8—+18 28] ai/si| P| | ci | ar) zesolun| 3_ 4 5 6 7 6 § 10 1_ 12 loess) 28.09 90:97 |22.07 [35.8 [30.95 19 | 20 | 21 | 22 | 23 | 24 | | 26 zo [30 | 31 | 32] 3a | a4 | 35 | 36 K |Ca | sc] |v | Cr | Mn| Fe Cu | 2n | Ga | Go| As | Se | Br | Kr 38.10 | 40.08 | 44.96 | 47:8 | 5094 | 52.00 | 54.96 | 55.5 63.85 | 65:30 [6072 [72.61 | 7492 7.96 | 78.00 | 3.80 37 | 38 | 39 | 40 | 41 | a2 | 43 | 44 a7 | 48 | 49 | 50 | 51 | 52 | 53 | 54 Rb | Sr | ¥ | Zr | Nb | Mo! Te | Ru Ag|Cd| in | Sn | Sb} Te | | | Xe 25.47 [87:82 2.91 [91.2 [92.91/96 96| 2) |101 1or9|1124 | 1148 | 11827 | 2181275 1269 [1313 $5 | 56 7 79 | a0 | 81 | a2 24 | 85 | 86 Ce | Be Au | Hg | TL | Pb | Bi | Po| At | Rn 323 |1373 197.0 200.6 | 204.4 |207.2 | 200.0| i200 | cro» | rzear ‘a7 | 88 m1 ]112 Fr Ra $ wz23) 2260 |227.0 272) 58 | 59 6 7 Co | Pr Te uy 140.1 |wos 1389 73.0 | 1780 90 791 7 103 Th, Pa Bk u 7320 |2910 2980 |297.0 coer | zen | cas | casa | eas | ase | zs [12600 | All atomic masses have been rounded off to four significant figures. Union for Pure and Applied Chemistry has not adopted official names or symbols forLIST OF NMR ACTIVE NUCLEI NUCLEUS | SPIN | ABUNDANCE H % 100% 7H or D 1 100 % *Li 1 7A Ti 1h 93% °B 3 20% “B 1% 80% Br 1% 51% Br 1% 49% %5CI 1% 75% Cl 1% 25% *C % 1% oF % 100% *p % 100 % "Ge | 4% 8% Nb 4% 100 % *Si % 47% Sn nn 8% Sn % 9% Xe % 26% *85Pt % 34% | Rh % 100 % "0 2% 0.037 % N % 0.365%