Chem 3810 Test 2 Fall 2005

Nov. 4th , 2005: 9:00 to 9:50 am Instructor: Dr. M. Gerken Time: 50 min Your name _______________ Student ID _______________ No. of pages: 4 +2

Answers

Answer all questions on the question sheet in the space provided. Q1 10 Question 1 (10 Marks) Draw the structures and specify the nature of the following hydrogen compounds ((i) ionic, hydridic, or protic, (ii) electron deficient, precise, or rich, (iii) Bronsted acid or base). Give a reaction equation for your acid/base assignment. (a) CsH Cs+ Hionic hydride hydridic hydrogen electron precise Bronsted base: H- + H2O H2 + OHQ2 23 Q3 10 Q4 10 Total 53 Percent 100 %

(b) AlH4-

H Al - H H H
covalent, hydridic hydrogen electron-precise Bronsted base: AlH4- + 4H2O 4H2 + Al(OH)41-6

Question 2 (23Marks) Phosphorus pentafluoride, PF5, is a pentagonal bipyramidal molecule with D3h symmetry. (a) Draw the MO diagram of PF5. As ligand orbitals, use only the p orbitals of fluorine (one orbital per fluorine) that point directly towards the phosphorus. You should distinguish between the three equatorial fluorines and the two axial fluorines. To find the SAOs for the latter ones, draw the symmetry-adapted linear combinations of the two axial ligand orbitals and think about the symmetry of the atomic phosphorus orbitals they would correspond to. Use only s and p valence orbitals on P. Dont forget to fill the AOs and MOs with electrons. (b) Label the MOs correctly. (c) How many bonding, non-bonding, and anti-bonding valence orbitals does PF5 have? (a) and (b)
PF5 2A2" P 3A1' 2E' A2" E' 2A1' 1E' A1' E' Feq Fax A1' A2" 5 F SAO 5F

A1'

1A2"

1A1'

s orbital on P A1'

pz orbital on P A2"

(c) four bonding MOs, one non-bonding MO, and four anti-bonding MOs 2-6

Question 3 (10 Marks) (a) Predict and draw the 19F and
31

P NMR spectra of PCl2F3 (non-fluxional). Consider chlorine as spin-

inactive in this test. Specify coupling constants in your spectra.

Fax Feq P Fax

Cleq Cleq
19

F: I=1/2, 100% and 31P: I=1/2, 100%

19

(b) Trigonal bipyramidal molecules can undergo Berry pseudo-rotation, a fluxional process that renders all ligands equivalent. Having this information, what would the Specify coupling constants in your spectra. (a)
19

F and

31

P NMR spectra look like?

F NMR spectrum:

Fax: a doublet (1J(31P-19Fax)) of doublets 2J(19Feq-19Fax),

and a doublet (1J(31P-19Feq)) of triplets 2J(19Feq-19Fax),

31

P NMR spectrum: a doublet (1J(31P-19Feq)) of triplets (1J(31P-19Fax))

2J(19Fax-19Feq) 1J(31P-19Fax) 1J(31P-19Feq)

19F

2J(19Fax-19Feq)

Fax
31P-spectrum

Feq

1J(31P-19Feq)

1J(31P-19Fax)

(b)

19 31

F NMR spectrum:

a doublet

1 1

J(31P-19F) J(31P-19F)
1J{31P-19F}

P NMR spectrum: a quartet

1J(31P-19F) 31P-spectrum

19F

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Question 4 (10 Marks) Predict and draw the two possible 19F NMR spectra of fluxional SbF5, i.e., only one fluorine environment. Specify the coupling constants in these spectra. Discuss the differences and the origin for the differences in these two spectra
19

F: I=1/2, 100% and 121Sb: I=5/2, 57% and 123Sb: I=7/2, 43%

If the quadrupolar relaxation is slow: a superposition of a 1:1:1:1:1:1:1:1 octet and a 1:1:1:1:1:1 sextet
1J(121Sb-19F) 1J(123Sb-19F)

if the quadrupolar relaxation is fast: a singlet, coupling information to the antimony is wiped out. If SbF5 is sufficiently symmetric the electric field gradient (efg) about Sb would be small and the quadrupolar relaxation would be small. In that case, we would be able to see coupling between fluorine and the quadrupolar Sb nuclei. However, SbF5 is quite unsymmetrical. Hence, both Sb nuclei relax very quickly and erase any coupling information in the 19F NMR spectrum.

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1
1.0079 hydrogen [2.1] 6.941
3Li 1H

Chem 3810 Standard Periodic Table Electronegativities are given in [ ] 2

9.0122
4Be

18
4.0026

13
10.811 boron [2.0] 26.9815
5B

14
12.011 carbon [2.5] 28.0855 silicon [1.8] 72.61
32Ge germanium 14Si 6C

15
14.0067 nitrogen [3.0] 30.9738
15P phosphorus 7N

16
15.9994 oxygen [3.5] 32.066 sulfur [2.5] 78.96
34Se 16S 8O

17
18.9984 fluorine [4.0] 35.4527 chlorine [3.0] 79.904
35Br 17Cl 9F

helium 20.1797
10Ne

2He

lithium berrylium [1.0] [1.5] 22.9898 24.3050 sodium [1.0] 39.0983

19K 11Na 12Mg magnesium

neon

39.948
18Ar

[1.2] 40.078
20Ca

3
44.9559
21Sc

4
47.88
22Ti

5
50.9415
23V

6
51.9961
24Cr

7
54.9380
25Mn

8
55.847
26Fe

9
58.9332 cobalt [1.7] 102.906
45Rh 27Co

10
58.693 nickel [1.8] 106.42
46Pd 28Ni

11
63.546 copper [1.8] 107.868
47Ag 29Cu

12
65.39 zinc [1.6] 112.411
48Cd 30Zn

aluminum [1.5] 69.723 gallium [1.7] 114.82

49In 31Ga

13Al

[2.1] 74.9216
33As

argon 83.80

potassium calcium scandium titanium vanadium chromium manganese iron [1.6] [0.9] [1.0] [1.3] [1.4] [1.5] [1.6] [1.7] 87.62 88.9059 91.224 92.9064 95.94 (98) 85.4678 101.07 rubidium strontium [0.9] [1.0] 132.905 137.327 cesium [0.8] (223) francium [0.8]
87Fr 55Cs 37Rb 38Sr

[1.9] 118.710 tin [1.8] 207.19

82Pb 50Sn

arsenic selenium bromine [2.1] [2.4] [2.8] 121.757 127.60 126.905 antimony tellurium [1.9] [2.1] 208.980 (210)
83Bi 84Po 51Sb 52Te

krypton [2.9] 131.29 xenon [2.3] (222)

86Rn 54Xe

36Kr

yttrium zirconium niobium [1.3] [1.4] [1.5] 178.49 180.948

39Y

40Zr

41Nb

molybdenum technetium

42Mo

[1.6] 183.85
74W

ruthenium rhodium palladium silver cadmium indium [1.6] [1.7] [1.7] [1.8] [1.8] [1.6] [1.6] 186.207 190.2 192.22 195.08 196.967 200.59 204.383
75Re

43Tc

44Ru

iodine [2.5] (210)

85At

53I

barium [1.0] (226.025) radium [1.0] 138.906

57La 88Ra

56Ba

La-Lu

hafnnium tantalum tungsten [1.3] [1.4] [1.5] (266) (262) (261)

72Hf

73Ta

rhenium [1.7] (264)

107Bh

osmium [1.9] (269)

108Hs

76Os

iridium [1.9] (268)

109Mt

77Ir

platinum [1.8] (271)

darmstadtium

78Pt

79Au

gold [1.9]

mercury [1.7]

80Hg

thallium [1.6]

81Tl

lead [1.7]

bismuth polonium astatine [1.8] [1.9] [2.1]

radon

Ac-Lr

rutherfordium

104Rf

dubnium seaborgium bohrium

105Db

106Sg

hassium meitnerium

110Ds

140.115
58Ce

140.908
59Pr

144.24

(145)

150.36

151.965

157.25

158.925 terbium (247)

97Bk 65Tb

162.50

164.930

167.26 erbium (257)

68Er

168.934
69Tm

173.04
70Yb

174.967
71Lu

lanthanum cerium (227.028) (232.038) (231.036) (238.029) (237.048) actinium9 thorium

89Ac 90Th
protactinium

60Nd 61Pm 62Sm 63Eu 64Gd praesodymium neodymium promethium samarium europium gadolinium

66Dy 67Ho dysprosium holmium

(244)
94Pu

(243)
95Am

(247)
96Cm

(251)

(252)

thulium ytterbium lutetium (259) (258) (262)

91Pa

uranium neptunium plutonium americium curium

92U

93Np

98Cf 99Es 100Fm 101Md 102No 103Lr berkelium californium einsteinium fermium mendelevium nobelium lawrencium

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