1

CONTENTS
Relative Atomic Masses of the Elements

Units, Symbols and Constants

The International System of Units (SI)
Recommended Values of Physical Constants

4
7

Selected Spectroscopic Data

Infrared
Characteristic Wavenumbers of Absorptions of
Organic Functional Groups
Anions and Cations
Coordination Compounds

8
11
11

Nuclear Magnetic Resonance

Properties of Selected NMR-Active Nuclides
Chemical Shifts of Common Functional Groups
13
C nuclei
1
H nuclei attached to saturated linkages
1
H nuclei attached to unsaturated linkages
1
H nuclei attached to heteroatoms
Additivity Table for 1H Chemical Shifts of Methylene Groups
SpinSpin Coupling Constants: 1H1H

13
14
15
15
15
16

Ultraviolet and Visible

Absorption Maxima of Substituted Benzene Rings
WoodwardFieser Rules for the Prediction of max Values
Electronic Absorption Characteristics of Transition Metal Complexes
Spectrochemical and Trans-Effect Series

17
18
19
19

Mass Spectrometry
Common Fragmentations and Fragment Ions

20

Symbols and Abbreviations Commonly Encountered in Organic Chemistry

21

The Proteinogenic Amino Acids

22

Group Theory
Symmetry Point Group Flow Diagram
Character Tables

23
24

Physical Definitions and Formulae

27

Mathematical Definitions and Formulae

The Greek Alphabet

28
31

The Periodic Table

32

12

RELATIVE ATOMIC MASSES Ar(E) ('ATOMIC WEIGHTS')

OF THE ELEMENTS
(Scaled to Ar(12C) = 12)
The atomic weights of many elements are not invariant but depend on the origin and treatment of the
material. The footnote to this Table elaborates the types of variation to be expected for individual
elements. The values of Ar(E) given here apply to elements as they exist naturally on Earth.
1

Hydrogen

1.00794

a,b,c

21

Scandium

Sc

44.955910

Helium

He

4.002602

a,c

22

Titanium

Yi

47.88

Lithium

Li

6.941

a,b,c

23

Vanadium

50.9415

Beryllium

Be

9.01218

24

Chromium

Cr

51.9961

Boron

10.811

a,b,c

25

Manganese

Mn

54.93805

Carbon

12.011

26

Iron

Fe

55.847

Nitrogen

14.00674

a,c

27

Cobalt

Co

58.93320

Oxygen

15.9994

a,c

28

Nickel

Ni

58.69

Fluorine

18.9984032

29

Copper

Cu

63.546

10

Neon

Ne

20.1797

30

Zinc

Zn

65.39

11

Sodium

Na

22.989768

31

Gallium

Ga

69.723

12

Magnesium

24.3050

32

Germanium

Ge

72.61

13

Aluminium

Al

26.98154

33

Arsenic

As

74.9216

14

Silicon

Si

29.0855

34

Selenium

Se

78.96

15

Phosphorus

30.973762

35

Bromine

Br

79.904

16

Sulfur

32.066

36

Krypton

Kr

83.80

a,b

17

Chlorine

Cl

35.4527

37

Rubidium

Rb

85.4678

18

Argon

Ar

39.948

38

Strontium

Sr

87.62

a,c

19

Potassium

39.0983

39

Yttrium

88.90585

20

Calcium

Ca

40.078

40

Zirconium

Zr

91.224

a,b

c
c
a,c
a

J. Emsley. The Elements, 3rd Edition, OUP, 1998.

Geologically exceptional specimens are known in which the element has an isotopic composition
outside the limits for normal material. The difference between the atomic weight of the element in
such specimens and that given in the Table may exceed considerably the implied uncertainty.

Modified isotopic compositions may be found in commercially available material because it has
been subjected to an undisclosed or inadvertent isotopic separation. Substantial deviations in atomic
weight of the element from that given in the Table can occur.

Range in isotopic composition of normal terrestrial material prevents a more precise Ar(E) being
given; tabulated Ar(E) value should be applicable to any normal material.

41

Niobium

Nb

92.90638

73

Tantalum

Ta

180.9479

42

Molybdenum

Mo

95.94

74

Tungsten

183.85

43

Technetium*

Tc

98.9062

75

Rhenium

Re

186.207

44

Ruthenium

Ru

101.07

76

Osmium

Os

190.2

45

Rhodium

Rh

102.90550

77

Iridium

Ir

192.22

46

Palladium

Pd

106.42

78

Platinum

Pt

195.08

47

Silver

Ag

107.8682

79

Gold

Au

196.96654

48

Cadmium

Cd

112.411

80

Mercury

Hg

200.59

49

Indium

In

114.82

81

Thallium

Tl

204.3833

50

Tin

Sn

118.710

82

Lead

Pb

207.2

51

Antimony

Sb

121.75

83

Bismuth

Bi

208.9804

52

Tellurium

Te

127.60

84

Polonium*

Po

209

53

Iodine

126.90447

85

Astatine*

At

210

54

Xenon

Xe

131.29

a,b

86

Radon*

Rn

222

55

Caesium

Cs

132.9054

87

Francium*

Fr

223

56

Barium

Ba

137.327

88

Radium

Ra

226.0254

57

Lanthanum

La

138.9055

89

Actinium*

Ax

227

58

Cerium

Ce

140.115

90

Thorium*

Th

232.0381

a,c,e

59

Praseodymium

Pr

140.90765

91

Protactinium*

Pa

231.03588

60

Neodymium

Nd

144.24

92

Uranium*

238.0289

a,b,e

61

Promethium*

Pm

145

93

Neptinium*

Np

237.0482

62

Samarium

Sm

150.36

94

Plutonium*

Pu

244

63

Europium

Eu

151.965

95

Americium*

Am

243

64

Gadolinium

Gd

157.25

96

Curium*

Cm

247

65

Terbium

Tb

158.92534

97

Berkelium*

Bk

247

66

Dysprosium

Dy

162.50

98

Californium*

Cf

251

67

Holmium

Ho

164.93032

99

Eisteinium*

Es

254

68

Erbium

Er

167.26

100

Fermium*

Fm

257

69

Thulium

Tm

168.93421

101

Mendelevium*

Md

258

70

Ytterbium

Yb

173.04

102

Nobelium*

No

259

71

Lutetium

Lu

174.967

103

Lawrencium*

Lr

260

72

Hafnium

Hf

178.49

a
a

a,c

Radioactive element that lacks a characteristic terrestrial isotopic composition.

An element, without stable nuclide(s), exhibiting a range of characteristic terrestrial compositions of

long-lived radio-nuclide(s) such that a meaningful atomic weight can be given.

Element has no stable nuclides.

UNITS and CONSTANTS

The International System of Units (SI)
Physical Quantity

Name of Unit

Symbol

Expression in terms of
SI base units

SI base units
length

metre

mass

kilogram

kg

time

second

electric current

ampere

thermodynamic temperature

kelvin

amount of substance

mole

mol

SI derived units
joule

m2 kg s2

force

newton

m kg s2 = J m1

pressure, stress

pascal

Pa

m1 kg s2 = N m2 = J m3

watt

m2 kg s3 = J s1

coulomb

sA

electric potential

volt

m2 kg s3 A1 = J A1 s1

electric resistance

ohm

m2 kg s3 A2 = V A1

electric conductance

siemens

m2 kg1 s3 A2 = 1

electric capacitance

farad

m2 kg1 s4 A2 = A s V1

magnetic flux

weber

Wb

inductance

henry

m2 kg s2 A2 = V s A1

magnetic flux density

tesla

kg s2 A1 = V s m2

frequency

hertz

Hz

s1

/ (T/K 273.15)

energy, work, heat

power
electric charge

Celsius temperature ()

degree Celsius

plane angle

radian

rad

solid angle

steradian

sr

m2 kg s2 A1 = V s

SI Prefixes
Fraction

Prefix

Symbol

Multiple

Prefix

Symbol

101

deci

10

deca

da

102

centi

102

hecto

kilo

10

milli

10

10

micro

10

mega

109

nano

109

giga

1012

pico

1012

tera

1015

femto

1015

peta

1018

atto

1018

exa

Decimal Fractions and Multiples of SI Units Having Special Names

Physical Quantity

Name of Unit

Symbol

Definition

ngstrm

1010 m = 101 nm = 100 pm

area

barn

1028 m2

volume

litre

1203 m3 = 1 dm3 = 1000 cm3

force

dyne

dyn

105 N

pressure

bar

bar

105 Pa

energy

erg

erg

107 J

kinematic viscosity

stokes

St

104 m2 s1

(dynamic) viscosity

poise

101 N s m2

maxwell

Mx

108 Wb

gauss

104 T

103 mol m3 = mol dm3

length

magnetic flux
magnetic flux density
concentration

Units Defined Exactly in Terms of the SI Units

Name of Unit

Symbol

Definitiona

length

inch

in

0.0254 m

mass

pound

lb

0.453 592 37 kg

time

minute

min

60 s

time

hour

3600 s

degree

(/180) rad

kilogram-force

kgf

9.806 65 N

pressure

standard atmosphere

atm

101 325 Pa

pressure

conventional millimetre
of mercuryb

mmHg

13.5951 9.806 65 Pa =
133.322 Pa

pressure

torr

Torr

(101 523/760) Pa = 133.322 Pa

pressure

bar

bar

105 Pa

pressure

pounds per square inch

psi

6894.757 Pa

energy

kilowatt hour

kW h

3.6 106 J

energy

thermochemical calorie

calth

4.184 J

debye

3.335 64 1030 C m

Physical Quantity

plane angle
force

electric dipole moment

a

These definitions are exact.

The difference between 1 mmHg and 1 Torr is less than 2 107 Torr.

Recommended Values of Fundamental Constants

Fundamental Constant

Symbol

Value

L, NA

6.022 1367 1023 mol1

8.314 510 J K1 mol1

k, kB

1.380 658 1023 J K1

F
( RT/F )

9.648 5309 104 C mol1

0.025 693 V

1.602 177 33 1019 C

electron volt

eV
LeV = FV

1.602 18 1019 J
9.648 547 104 J mol1

Planck constant

h
h = h/2

6.626 0755 1034 J s

1.054 5726 1034 J s

speed of light in vacuuma

2.997 924 58 108 m s1

permeability of a vacuuma

4 107 A2

permittivity of a vacuuma

8.854 187 816 1012 F m1

rest mass of electron

me

9.109 3897 1031 kg

rest mass of proton

mp

1.672 6231 1027 kg

Hartree energy

Eh

4.359 7482 1018 J

Bohr radius

a0

5.291 772 49 1011 m

Bohr magneton

B = eh/4 me

9.274 0154 1024 J T1

nuclear magneton

= eh/4 mp

5.050 7866 1027 J T1

Rydberg constant

109 737.315 34 cm1

unified atom mass unit

1.660 54 1027 kg

gravitational constant

6.67259 1011 m3 kg1

standard acceleration due to gravitya

9.806 55 m s2

Avogadro constant
gas constant
Boltzmann constant
Faraday constant at T = 298.15 K
elementary charge

These values are exact.

SPECTROSCOPIC DATA
INFRARED
Characteristic Wavenumbers, ~ , of Fundamental Absorptions of Organic Functional Groups

~ /cm1
1.

2.

3.

OH stretching
free

sharp

36503590

intramolecular hydrogen-bonded single bridges

(excluding chelates)

sharp

36003450

intermolecular hydrogen bonded polymeric associations

broad

34003200

intermolecular chelates and carboxylic acids

broad

32002500

primary amides

two bands

~3500 and 3400

primary amines

two bands

35003300

NH stretching (hydrogen bonding lowers as in OH stretching)

secondary amides

34603400

secondary amines

34503300

CH stretching
alkynes

3300

alkenes and aryls

methyls and methylenes

30403010
two or three bands

aldehydes
4.

5.

29602850
29002700

CX stretching
nitriles

22602220

alkynes

22602100

X=Y=Z stretching
allenes C=C=C

~1950

azides RN=N+=N
carbon dioxide O=C=O
6.

C=O stretching

(a)

Aldehydes

21602120
antisymmetric

2349

saturated

17401720

aryl

17001650

,-unsaturated

17051680
table continued on next page

9
Characteristic wavenumbers, ~ , of fundamental absorptions of organic functional groups (continued)

~ /cm1

C=O stretching continued

(b)

(c)

(d)

(e)

Ketones
four ring

~1780

five ring

17501740

saturated acyclic, alicyclic six-ring and larger, and ,-unsaturated five ring

17251705

aryl

17001680

,-unsaturated

16851660

Carboxylic acids
saturated

17251700

,-unsaturated

17151690

aryl

17001680

most carboxylate anions

16101550

Esters and lactones

esters of phenols or enols

18001750

five-ring lactones

17801760

,-unsaturated five-ring lactones

17701740

saturated esters and six-ring and larger lactones

17501735

esters of aromatic or ,-unsaturated acids

17301715

Amides and lactams

primary amides

two bands

~1690 and 1600

primary amides (solid phase)

two bands

1650 and 1640

secondary amides

two bands

17001670 and 15501510

secondary amides (solid phase)

two bands

16801630 and 15701515

tertiary amides

(f)

(g)

7.

16701630

four-ring lactams

~1745

five-ring lactams

~1700

six ring and large lactams

~1670

Anhydrides
saturated

two bands

18501800 and 17901740

aryl and ,-unsaturated

two bands

18301780 and 17701710

Acid chlorides
saturated

18151790

aryl and ,-unsaturated

17901750

C=N stretching
imines and oximes

variable and of little diagnostic value

~16901640
table continued on next page

10
Characteristic wavenumbers, ~ , of fundamental absorptions of organic functional groups (continued)

~ /cm1
8.

C=C stretching
isolated
conjugated
aromatic
aromatic

9.

16801620

one or two bands

16501590

two bands

~1600 and 1500

weak or absent when ring is not further conjugated

1580

N=O stretching
Nitro compounds

10.

variable

asymmetric

15551540

symmetric

13851350

Carbonhalogen stretching
CF

14001000

CCl

800 600

CBr

600500

CI
11.

500

CH deformations
i-propyl

13851380 13701365
11751165 11701140

t-butyl

13951385

1365

12551245 12501200
RCH=CH2

12.

14.

915905

RCH=CHR (trans)

970960

R2C=CH

895885

R2C=CHR

840790

RCH=CHR (cis)

~690

RCCH

~630

NH bend
primary amines and amides

13.

995985

16501560

PX stretching
PH

24402350

PPh

1440

POR

12401030

P=O

13001250

BH stretching
terminal BH

26502450

bridging BH

20901600

11

Characteristic Wavenumbers, ~ , of Fundamental Absorptions of Anions and Cations

~ /cm1
ammonium

[NH4] +

33003030 14301390

cyanide

[CN]

thiocyanate

[SCN]

22002000

acetate

[CH3CO2]

acetate

[CH3CO2]

CN stretch

21502050

COO antisymmetric stretch

15801550

COO symmetric stretch

14301410

carbonate

[CO3]

14901410

nitrate

[NO3]

13801350

11701050

sulfate

[SO4]

11301080

phosphate

[PO4] 3

11001000

perchlorate

chromate

[ClO4]

[CrO4]

885

N-bonded thiocyanate

CS stretch

860780

S-bonded thiocyanate

CS stretch

720690

Characteristic Wavenumbers, ~ , of Fundamental Absorptions in Coordination Compounds

~ /cm1
Transition metal carbonyls: Wavenumber ranges of these CO stretching
vibrations apply only to unsubstituted, neutral species. Actual values depend
also on the compound and the nature of other ligands attached to the metal.
terminal CO

21501900

bridging CO

19001750

triply bridging or capping CO

18001600

MetalX stretching modes

MH

22501700

M=O

1050950

MF

750500

MCl

400200

MBr

300200

MI

200100

12

NUCLEAR MAGNETIC RESONANCE

Properties of Selected NMR-Active Nuclides
Natural Abundance
C

/ 107 rad T1 s1

Relative Receptivity
values for I= nuclei
are 3C

99.985%

1/2

26.75

1.00

H, D

0.015%

4.11

1.45 106

10

19.58%

2.87

3.93 103

11

80.42%

3/2

8.58

0.133

13

1.108%

6.73

1.76 104

14

99.63%

1.93

1.00 103

15

0.37%

1/2

2.71

3.85 106

17

0.037%

5/2

3.63

1.08 105

100%

1/2

25.18

0.834

Na

100%

3/2

7.08

9.27 102

100%

5/2

6.98

0.207

4.70%

1/2

5.32

3.69 104

100%

1/2

10.84

0.067

Se

7.58%

1/2

5.12

5.30 104

Rh

100%

1/2

0.85

3.16 105

107

Ag

51.82%

1/2

1.09

3.48 105

109

Ag

48.18%

1/2

1.25

4.92 105

Nuclide

1
2

19
23

27

Al

29

Si

31
77

103

117

Sn

7.61%

1/2

9.58

3.49 103

119

Sn

8.58%

1/2

10.02

4.51 103

Xe

26.44%

1/2

7.44

5.69 103

14.40%

1/2

1.12

1.06 105

Pt

33.8%

1/2

5.77

3.39 103

Hg

16.84%

1/2

4.82

9.82 104

129

183

195
199

13

Chemical Shifts of Common Functional Groups

Positions of 1H- and 13C-NMR signals in the following tables are given as chemical shifts, ,
expressed as parts per million, ppm, relative to tetramethylsilane, TMS. Usual ranges of values
for 1H-NMR are 015, except that most MH shifts are < 0. For 1H-NMR, values are usually
within 0.2 of those quoted unless inductive, anisotropic or steric effects associated with functional
groups operate. Chemical shifts for 13C-NMR are usually 0250.

Chemical Shifts of 13C Nuclei in Common Functional Groups

Alkanes

Ethers

Cyclopropanes

08

CH3O

4560

Cycloalkanes

525

RCH2O

4270

RCH3

525

R2CHO

6577

RCH2R

2245

R3CO

7083

R2CHR

3058

R3CR

2850

Amines

CH3N

1045

RCH2N

4555

RCOOR

160177

R2CH2N

5070

RCOOH

162183

R3CN

6075

RCHO

185205

RCOR

190220

Carbonyls

Other Heteroatoms

RCH2S

2242

Halogens

RCH2P

1025

CH3X

525

ArP

120130

RCH2X

538

ArN

130138

R2CHX

3962

ArO

130150

R3CX

3575

RCN

118123

Unsaturated Compounds

Aromatics

110133

Alkenes

100143

Alkynes

7595

14
Chemical Shifts of Methyl, Methylene and Methine Protons Attached to Saturated Linkages
Methyl

Methylene

Methine

CH3C

0.9

CH3CC=C

1.1

CH3CO

1.4

CH2C

1.4

>CHC

1.5

CH3C=C

1.6

CH2CC=C

1.7

CH3CONR

2.0

CH2CO

1.9

CH3C=CCO

2.0

CH3COOR

2.0

CH3S

2.1

CH3COR

2.2

CH2COOR

2.2

CH3I

2.2

CH2CONR

2.2

CH3CHO

2.2

CH2CHO

2.2

CH3Ar

2.3

CH2C=C

2.2

CH3N

2.3

CH2CN

2.3

CH3COOAr

2.4

CH2COR

2.4

CH2S

2.4

CH2C=CCO

2.4

CH2N

2.5

CH2Ar

2.6

CH3COAr

2.6

CH3Br

2.6

CH3NCOR

2.9

CH3NAr

3.0

CH3Cl

3.0
CH2I

CH3OR

3.3

CH3N

3.3

CH3OH

3.4

3.2

CH2OR

3.4

CH2Br

3.5

CH2Cl

3.6

CH2OH

3.6

>CHCO

>CHCHO

2.4

>CHCOR

2.7

>CHCN

2.7

>CHN

2.8

>CHAr

3.0

>CHS

3.2

>CHCOAr

3.3

CH3OCOR

3.7

>CHOR

3.7

CH3OAr

3.8

>CHOH

3.9

CH3OC=C

3.8

>CHCl

4.0

>CHBr

4.1

>CHI

4.2

>CHOCOR

4.8

CH2OCOR
CH2OAr

4.1
4.3

Chemical Shift Ranges of Protons Attached to Unsaturated Linkages

Proton

Proton

CCH

1.83.1

C=CHO

6.08.1

CH=CN

3.75.0

Aromatic protons

6.09.0

CH=C=O

4.05.0

CH=CCO

6.57.8

C=CH

4.56.0

HCOO, HCON

8.08.2

C=CHN

5.78.0

RCHO, ArCHO

9.410.5

C=CHCO

5.86.7

Chemical Shift Ranges of MH, OH and NH Protons

Range

Group
MH (M = Transition metal)

300

Diagnostic of metal hydride

ROH

210

H-bonded enols usually in range 1116

RNH2 RNHR'

25

Position depends strongly on solvent

ArNH2, ArNHR'

3.56 or larger

RCONH2

58.5

RCONHCOR'

9ca. 12

RCO2H

10ca. 13

Often very broad (sometimes unobservable)

Often very broad

Additivity Table for Estimation of the 1H Chemical Shifts of Methylene Groups

(CH2X1X2) = 1.25 + X1 + X2
substituent

Xn

substituent

Xn

sustituent

Xn

alkyl

0.0

OCOR

2.7

SH, SR

1.0

vinyl

0.8

NH2, NR2

1.0

SO2R

1.7

alkynyl

0.9

NO2

3.0

-CHO

1.2

phenyl

1.3

2.1

-COR

1.2

OH

1.7

Cl

2.0

-CO2H

0.8

OR

1.5

Br

1.9

-CO2R

0.7

OPh

2.3

1.4

-CN

1.2

16

H1H SpinSpin Coupling Constants

J / Hz

J / Hz

8 to 18a

CH

CH

03

CH

13

68b

CH

CH2

68b

CH

CH

68b

CH

H 3C

CH

46

CH

H3C
CH

CH

02

H3C

Ha

Heq
Heq

aa

813

ae

26

ortho

69

meta

13

para

01

cis

512

trans

1218

gem

3 to
+3a

ee

Ha

26
H

CH

411

CH

H
C

CH

CH

613

H
H
C

CH

CH

58
H

The sign of J is unimportant for first-order spectra.

Assumes free rotation.

17

ULTRAVIOLET and VISIBLE

Absorption band intensities are expressed in terms of the molar absorption coefficient
=

A
cl

where A = dimensionless absorbance, c = molar concentration, and l = path length of the

absorbing species. Units of may therefore be mol1 dm3 cm1 or 103 cm2 mol1.
Absorption bands with maxima, max, below 215 nm are observable only as end absorption.
Compounds containing unconjugated -bands show only end absorption. Saturated aldehydes
and ketones do, however, show a low-intensity band with max = 1030 mol1 dm3 cm1 in the
range 275295 nm.

Absorption Maxima of Substituted Benzenes PhR

solvent: H2O or MeOH
max

max

/ nm

/ mol1
dm3 cm1

203

NH3

max

max

/ nm

/ mol1
dm3 cm1

7400

254

204

203

7500

254

160

Me

206

7000

261

225

Cl, Br

210

7700

262

190

OH

210

6200

270

1450

OMe

217

6400

269

1480

SO2NH2

217

9700

264

740

CN

224

13000

271

1000

224

8700

268

560

CO2H

230

11600

273

970

NH2

CO2

230

8600

280

1430

235

9400

287

2600

NHAc

238

10500

CH=CH2

248

1400

282

750

NO2

268

7800

(E)-CH=CHCO2H

273

21000

max
/ nm

291

max

/ mol1
dm3 cm1

500

18
WoodwardFieser Rules for the Prediction of max Values for * Transitions
of Dienes, Polyenes and ,-Unsaturated Aldehydes, Ketones and Acids
max (EtOH) / nm

Basic Chromophore: Diene

Diene

214
Increment / nm

Each additional double bond extending the conjugation

30

Each homoannular diene

The exocyclic nature of any double bond

39
b

Each alkyl group or ring residue

Each auxochrome:

OAcyl

OAlkyl

SAlkyl

30

Cl, Br

NAlkyl2

60

Basic Chromophore: , -unsaturated Aldehydes, Ketones and Acids

max (EtOH) / nm

Six-ring or acyclic ,-unsaturated ketone

215

Five-ring ,-unsaturated ketone

202

,-unsaturated aldehyde

209

,-unsaturated acid

197
Increment / nm

Each additional double bond extending the conjugation

30

Each homoannular diene

The exocyclic nature of any double bond

39
b

10

12

18

35

30

50

OAcyl

, ,

OAlkyl

35

30

17

31

SAlkyl

85

Cl

15

12

25

30

95

Each alkyl group or ring residue

for aldehydes and ketones only
Each auxochrome:

OH

Br
NAlkyl2
a

Homoannular diene:

Exocyclic double bond:

19

Typical Electronic Absorption Intensities of Transition Metal Complexes

max / mol1 dm3 cm1

Type of Transition
Spin-forbidden, Laporte forbidden

0.011.0

Spin-allowed, Laporte forbidden

1.0100

Spin-allowed, Laporte forbidden, but with dp mixing (Td symmetry)

and/or intensity stealing

1001000

Spin-allowed, Laporte allowed; charge transfer

> 1000

Spectrochemical Series
Common Ligands
I < Br <Cl < S2~ SCN <F < OH < O2 ~ H2O < NCS < py < NH3
< ethylenediamine (en) < bipyridine (bipy), PR3 < CH3 < CN CO
Metal Ions
Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Cr3+ < V3+ < Co3+
< Mn4+ < Mo3+ < Rh3+ < Ru3+ < Pd4+ < Ir3+ < Re4+ < Pt4+
o values for metals of the first transition series are typically in the ranges M2+: 700016000 cm1
and M3+: 1300026000 cm1 for all but the strongest ligands.
In any group o increases with atomic mass of the metal, i.e. 3d < 4d < 5d.
For tetrahedral complexes, t

4
9

o .

(3+ ion) 23 (2+ ion) for isoelectronic ions.

The Trans-Effect Series
CN , CO > PR3, H > CH3 > C6H5 > NO2 , I > Br > Cl > py, NH3 > OH > H2O

20

MASS SPECTROMETRY
Common Fragmentations and Fragment Ions in Mass Spectrometry
Common Fragmentations
m/z

Fragment Lost

M 3 to M 14

Inference
highest mass peak observed is itself a fragment and not a molecular ion

M 15

CH3

M 17

OH

alcohol or carboxylic acid

NH3

primary amine, odd molecular weight

M 18

H2O

alcohol, aldehyde, ketone

M 26

C2H2
CN

nitrile, odd molecular weight

M 31

CH3O

M 35 or M 37

Cl

M 43

CH3CO

M 58

methyl ester or ether

a molecular ion consisting of two peaks of intensity 3:1, two mass
units apart, indicates a monochloro compound
methyl ketone

CH2=C(OH)CH3 McLafferty rearrangement, methyl ketone with -hydrogen

M 77

C6H5

M 79 or M 81

Br

M 91

C7H7

M 105

C6H5CO

M 127

monosubstituted
a molecular ion consisting of two peaks of equal intensity, two mass
units apart, indicates a monobromo compound
benzylic
aromatic ketone or ester

Fragment Ions
m/z

Fragment

18

H2O+

28

CO+, C2H4+, N2+

30

CH2NH2+

primary amine, odd molecular weight

31

CH2OH+

primary alcohol

57
58

C4H9

Inference

tert-butyl group

CH2=C(OH)CH3 methyl ketone

65

C5H5+

77

C6H5

monsubstituted aromatic

C7H7

tropylium ion, usually the base peak

91

secondary fragment from tropylium ion

SYMBOLS AND ABBREVIATIONS COMMONLY ENCOUNTERED IN ORGANIC CHEMISTRY

Groups
R

alkyl

generalised alkyl group

Me

methyl

CH3

Et

ethyl

CH2CH3

Pr

propyl

CH2CH2CH3

i-Pr

isopropyl

CH(CH3) 2

Bu, n-Bu

butyl

CH2CH2CH2CH3

i-Bu

isobutyl

CH2CH(CH3) 2

s-Bu, sec-Bu

sec-butyl

CH(CH3)CH2CH3

t-Bu, tert-Bu

tert-butyl

C(CH3)3

Ar

aryl

generalised aromatic ring

Ph ()

phenyl

C6H5

Ac

acetyl (ethanoyl)

COCH3

Bn

benzyl

CH2C6H5

Boc, BOC or t-Boc

t-butoxycarbonyl

COOC(CH3)3

Bz

benzoyl

COC6H5

Ms

mesyl (methanesulfonyl)

SO2CH3

Tf

triflyl (trifluoromethanesulfonyl)

SO2CF3

Ts

tosyl (toluenesulfonyl)

SO2C6H4CH3 (para)

TMS

trimethylsilyl (or tetramethylsilane in NMR)

Si(CH3)3

TBDPS

tert-butyldiphenylsilyl

SiPh2C(CH3)3

TBS

tert-butyldimethylsilyl (also seen as TBDMS)

Si(CH3)2C(CH3)3

THP

tetrahydropyranyl

benzyloxycarbonyl or Cbz

C6H5CH2OCO

Reagents, Solvents and Others

aq.
n-BuLi or nBuLi
cat.
D

aqueous

HMPA

hexamethylphosphoramide

n-butyllithium

light

catalyst or catalytic

IR

infrared

deuterium

LDA

DIBAL

diisobutylaluminium hydride

DMAP

4-dimethylaminopyridine

NMR

nuclear magnetic resonance

DMF

N,N-dimethylformamide

PCC

pyridinium chlorochromate

dimethyl sulfoxide

PDC

pyridinium dichromate

DMSO

mCPBA

lithium diisopropylamide

DCM

dichloromethane

Et2O

diethyl ether

TFA

trifluoroacetic acid

electron impact (ionisation)

THF

tetrahydrofuran

EI
FAB

fast-atom bombardment

TBAF

meta-chloroperoxybenzoic acid

tetra-n-butylammonium fluoride

heat

THE PROTEINOGENIC AMINO ACIDS

R H

R H

For the generalised L-amino acid structure:

H2N

or in zwitterionic form

CO2H

H3N

All have S absolute configuration except cysteine which is R

Amino Acid

Amino Acid

Glycine (Gly or G)

H-

Cysteine (Cys or C)

Alanine (Ala or A)

CH3-

Valine (Val or V)

H3C

R
HS

H3CS

Methionine (Met or M)

HN

CH3

Histidine (His or H)

CH3

Leucine (Leu or L)

Isoleucine (Ile or I)

H2N

Lysine (Lys or K)

H3C

CH3
H

H3C

H
N

H2N

Arginine (Arg or R)

NH

Phenylalanine (Phe or F)

HO2C

Aspartic acid (Asp or D)

HN

Tryptophan (Trp or W)

HO2C

Glutamic acid (Glu or E)

HO

Serine (Ser or S)

Threonine (Thr or T)

Asparagine (Asn or N)

CH3
OH

H2N

H2N

Glutamine (Gln or Q)

HO

Tyrosine (Tyr or Y)

L-Proline:
Proline (Pro or P):

N
H

H
CO2 H

or

N
H2

H
CO2

CO2

23

24

GROUP THEORY
Character Tables
CS = Ch

A'

x, y, Rz

x2, y2, z2, xy

A"

z, Rx, Ry

yz, xz

C2v

C2

v(xz)

'v(yz)

A1

x2 , y2 , z2

A2

Rz

xy

B1

x, Ry

xz

B2

y, Rx

yz

C3v

2C3

3v

A1

A2

Rz

x2 + y 2 , z2

(x, y), (Rx, Ry)

C4v

2C4

C2

2v

2d

A1

A2

Rz

B1

B2

(x2 y2, xy) (xz, yz)

x2 + y 2 , z2
x2 y2
xy

(x, y), (Rx, Ry)

(xz, yz)

x2 + y 2 , z2

C5v

2C5

2C52

5v

A1

A2

Rz

E1

2 cos 72 2 cos 144

E2

2 cos 144 2 cos 72

(x, y), (Rx, Ry)

(xz, yz)
(x2 y2, 2xy)

25

D2h

C2(z)

C2(y)

C2(x)

v(xy)

v(xz)

v(yz)

Ag

B1g

Rz

xy

B2g

Ry

xz

B3g

Rx

yz

Au

B1u

B2u

B3u

D3h

2C3

3C2

2S3

3v

A'1

A'2

E'

A"1

A"2

E"

(Rx, Ry)

x2 + y2 , z2
Rz
(x2 y2 , 2xy)

(x, y)

2S4

2v

2d

A1u

A2u

B1u

B2u

Eu

D4h

A1g

A2g

B1g

B2g

Eg

2C4 C 2

2C'2 2C"2

x2 , y2 , z2

(xz, yz)

x2 + y 2 , z2
Rz
x2 y2
xy
(Rx, Ry)
z

(x, y)

(xz, yz)

26

D2d = Vd

2S4

C2

2C'2

2d

A1

A2

B1

B2

xy

(x, y), (Rx, Ry)

(xz, yz)

Cv

C2

2C

A1 +

A2

E1

2 cos

E2

2 cos 2

E3

2 cos 3

Dh

2C

x2 + y 2 , z2
Rz
x2 y2

x2 + y2 , z2

z
Rz
(x, y), (Rx, Ry)

(x2 y2, xy)

2S

2 cos

2 cos

2 cos 2

2 cos 2

C2

2 cos

2 cos

2 cos 2

2 cos 2

u
u

x2 + y 2 , z2

(xz, yz)

Rz
(Rx, Ry)

(x2 y2, 2xy)

(xz, yz)

z
(x, y)

27

PHYSICAL DEFINITIONS AND FORMULAE

Classical Mechanics

F =m a

F = force, m = mass, a = acceleration

W =F x

W = work done, F = force, x = distance moved

p=m v

p = momentum, m = mass, v = velocity

T = 12 m v 2 =

P=

p2
2m

T = kinetic energy, m = mass, v = velocity,

p = momentum

F
A

P = pressure, F = force, A = area

mg
A

P = pressure, m = mass,
g = acceleration due to gravity, A = area

m
V

= density, m = mass, V = volume

P=

=
P=

Newtons Second Law

P = pressure exerted by a column of density and

height h where g = acceleration due to gravity,
A = area, V = volume

mg V g
=
=gh
A
A

Electrical Energy

V =I R
E =V I t =
W=

Ohms Law

V2t 2
= I Rt
R

V = electrical potential I = current, R = resistance

E = energy, V = electrical potential I = current,
t = time, R = resistance

E
t

W = power, E = energy, t = time

Electrostatics

V=

q1 q2
4 0 r

F=

q1 q2
4 0 r 2

Coulombs Law

V = potential energy of two charges q1 and q2

separated by r, for a medium of permittivity, 0

F = force acting between two charges q1 and q2

separated by r, for a medium of permittivity, 0


















 




 









 
    
 
  
    
 
  
 

    
 
  
    
 
  

     



      



      




 







 



  

 

  

              
 
   

              
  
  
 

     

















 

  


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32

PERIODIC TABLE OF THE ELEMENTS

1

H
3

He
4

Li Be
11

12

13

Na Mg
19

20

38

Rb Sr
55

56

21

22

39

Y
57

40

23

24

25

26

27

88

C
14

N
15

89

28

29

30

31

32

O
16

P
33

10

F Ne
17

S
34

Cl Ar
35

41

42

43

44

45

46

47

48

49

50

51

52

104

36

53

Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te
72

18

V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
73

74

75

76

77

Cs Ba La Hf Ta W Re Os Ir
87

Al Si

K Ca Sc Ti
37

105

106

107

108

78

79

80

81

82

83

84

54

I
85

59

60

61

62

109

63

64

65

66

67

68

69

70

71

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90

91

92

93

94

95

86

Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac Rf Db Sg Bh Hs Mt
58

Xe

96

97

98

99

100

101

102

103

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr