This presentation is 15 years old and

without the spoken accompaniment it is

difficult to follow. However, some of the
slides might be useful.
Definition of the Class
of a Covalent Compound

M= is the element whose

compound is to be classified

The general class of ALL

compunds of M is given by

ML X Z
l x z
 Definit ions of Ligand Class

Monof unct ional Ligands.

The f unc t ions are in class X, L, or Z.

1 ) The X-class.
An X ligand f unct ion donat es one elect ron
t o t he f ormat ion of t he bond.

2 ) The L-c lass.

An L ligand f unnc t ion donat es r wo
elec t rons t o t he f ormat ion of t he bond.

3 ) The Z-c lass

A Z ligand donat es NO elec t rons t o t he
f ormat ion of t he bond BUT r ec eiv es TWO
elec t rons f rom t he bond
 -bond dative -bond acceptor -bond
Mo L
L Mo Z
Mo X
Mo L Mo Z
Mo X
Class X Class L Class Z

dative -bond acceptor -bond

-bond
+ + + + + +

Mo X Mo L Mo Z
_ _ _ _

Mo X Mo L Mo Z
Class X Class L Class Z

a -bond, X-function
a -bond, X-function a -bond, X-function a -bond, X-function

+ + R + + R
_

Mo C Mo N Mo O
R
_ _ R _ _
+ +
a -bond, X - function a-bond, L-function a -bond, L-function

Mo C Mo N Mo O

Class LX Class LX 2
Class X 2

(i) (ii) (iii)

Mono- and poly-functional Ligands

 O O CH
3
S C
O O O O E E

Mo Mo Mo
2
-acetato
 2-sulphato E = PR2 , NR2 , SR, OR
Class X 2 Class LX Class L2

X
X H Mo
Mo Mo Mo Mo Mo
X = Cl, Br, I, SR, NR -hydrido Mo
2
X = O, S, Se
Class X-- -L Class X -- L
Class X2- 2- L
(i)

+ + +
+
Mo O Mo + O
_
O _ Mo +
_ _ _ Mo
_
Mo Mo O
Mo O Mo Mo Mo
linear bent
Class X--X Class LX---LX Class LX---LX

(ii) (iii)

Figure 3. Examples of polydentate and bridging ligands

 Z X
X X L X

L L L L L
ethylene -allyl -cyclopropenyl -butadiene -cyclobutadiene
Class L Class L X Class X 3 Class L 2 Class LX 2

E
N
E
R
G
Y
Z X
X X
X L L L
L L L L
L L L L
-cyclopentadienyl -benzene -cycloheptatrienyl -cyclooctatetraene
Class L X Class L 3 Class L 2 X 3 Class L3X2
2
 S S S
S S S
HC HC CH HC HC S
or CH
H C Mo Mo
HC HC H C
CH (i) CH
S S
S S S S
trigonal prism or trigonal prism
MoX6 MoL6

or
Mo Mo
(ii)

MoL3 X6 or MoL6

one of 12 p-
Cl Cl Cl 3-
orbitals on 6 F atoms
M M F
Cl Cl Cl
Cl Cl Cl F F
Mo
M = Cr ML3 X3 , 3 upe F
F
M = Mo ML3 X3 + x
M = W ML3 X6 diamagnetic, F
W W
(iii) (iv)

+
or Mo O O + O
Mo O or
R R Mo Mo
3 sp 2OR is
sp OR sp O is sp2 O is
is class X class LX class LX 2 class X2
(v) (vi)

Figure 5. Non-innocent ligand systems.

Table 8. Exa mples of ligand s with poly-functional ligating atoms.
Ligand Class Representatio Examples.
n
O X2 M= O CO2, [Mo(-C5H5)2O], OsO4, MoCl2O2

S X2 M= S [MoS4]2-, CS2

NR X2 M = NR RC = NR

CR2 X2 M = CR2 H2C = CH2, [Ta(-C5H5)2(=CH2)Me]

CR X3 M C HC  CH, Mo( CR)Br(CO)4

N X3 M N N2, (PR3)4Re(N)Cl2a

NO X Lb M—NO NO in Cr(NO)4, Co(CO)3NO

Cl4Re X4 M M [Cl4Re  ReCl4]2-

a Re-N = 1.79Å b For reduction to E.Q.N. is X LL2
Terminal ligands Bridging two atoms Bridging three atoms
_ 2_ _ 3=


Class L.N. Class L.N. Class L.N.

X 1 O X_ _ X 2 O
L_  = X 4
O
2
H
H
H
L 2
O X_  _ L 3 O _
X  = L2 5 O
H
H
H H
L_ _L _ + O
X2 2 O 4 O XL  = LX 6
-
+ + Bridging four atoms
XL 3 O X _  _X L 4 -O 4
= =
- H -+
+
X2L 4 O X L__ LX 6
- +O O

- -+ 4
L2 =  = X
2
L.N. 6

Figure 12. Classification of ligands found in aqueous systems

Table 1.Typical ligands found in molybdenum chemistry classified according to the
number of electrons required for bonding (x), the number of electrons donated to
the molybdenum (L.N.) and the LlXxZz class.‡

Examples
x L.N. Class
Electrons Electrons
required donated to
by ligand metal by the
ligand

2 0 Z BH3, BF3, BCl3, BR3, B(C6F5)3, AlMe3, SiF4, (generally, Lewis

acids)

1 1 X H

1 1 CR3, -CR=CR2, -CCR, -COR, -C 6H5,

1-CH2CH=CH2, -C5H5, CF3, C6F5, CH2CMe3, CH2SiMe3,
CH2CMe2Ph

1 1 NR2, OR, -OOR, F

1 1 SiR3, -PR2, SR, Cl

1 1 GeR3, AsR2, SeR, Br

1 1 SnR3, I

1 1 CN, SCN, NCS, N3, OCN, NCO, OS O2R, ONO, ONO2, OClO3,
OSiR3

1 1 Mn(CO)5, Fe(-C5H5)(CO)2, Mo(-C5H5)(CO)3, Au(PPh3),

HgCl,
 Examples
x L.N. Class
Electrons Electrons
required donated to
by ligand metal by
the ligand
bidentate with mono-functional ligating atoms,
2 2 X2 -SCH2CH2S-, oxalato, o-quinones, -(S)2-, SO4, CO3, -
(O)2-, metallacycles -(CH2)n-,, where n = 2*, 3 or 4

2 2 X2 monodentate with poly-functional ligating atoms, =CR2,

=NR*(bent) , =O*, =S, =C=CR2,

0 2 L NH3, NR 3, OH2, OR2, PR 3, P(OR)3, SR2, SeR2, AsR3

0 2 CO, H2C=CH2, R2C=CR2, RC=CR, S=CR2, N2, PF 3

0 2 T.H.F., Et2O, DMSO, RCN, RNC, py

0 2 L-function of X--L-ligands, e.g. in bridging Cl. Also

the half-arrow function of agostic hydrogen, see Figure 3
(i).
V.N. L.N. Class Examples
x Electrons
donated

3 3 X3 Tridentate with 3 monofunctional X-ligating atoms. None known

3 3 X 3† Monodentate with one tri-X-functional ligating atom, CR, N

1 3 XL -CH5 (generally -allylic systems,) acac, dmg,

2-acetato, -O2CR, -S2CR, -S2CNR2, -S2PR 2,
NH2CH2CO2- (amino acids), BF4, BH4,

1 3 X L† NO, NR 2 (in planar MNR2 amido systems)

4 4 X4 MoX2L2, e.g. in [Mo 2Cl8]4-

2 4 X 2L -C4H4, (generally -cyclobutadiene derivatives)

2 4 X 2L NR (linear imido ligands)

0 4 L2 -C4H6, (dienes generally)*, bipyridyl, o-phenanthroline,

ethylenediamine RS(CH) 2SR, diphosphines, e.g.

diphos(dppe)
 x L.N. Class Examples
Electrons Electrons
required donated

3 5 LX3 N(CH2COO)3

1 5 L2 X -C5H5, dienyls generally

2 6 L2 X 2 1,5,-diazacyclooctane-N,N'-diacetate (dacoda)

0 6 L3 6-Benzene, (6-arenes generally), 6-C7H8,

6-COT, RSi(CH2PMe2)3

1 7 L3 X None known

3 7 L2 X 3 -C7H7

4 8 L2 X 4 edta

2 8 L3X2 -COT, -C5H4(CH2)3NR

-C5H4(CH2)3N= (linear imido)

3 9 L3 X 3

0 12 L6 {FB(ONCHC5H3)3P} , P(bipy)3
How t o det ermine t he class of compounds
of M which are cat ions or anions
Rule 1 .
X and 1 e = X- = L
1+ 1 2

Rule 2
Lless 1 e = L+ = X
2 - 1 1

Rule 3. when no X available

t hen L+ 1e = L- = LX
2 + 1 = 3

Rule 4. X+ = Z
1-1= 0
 Table 7. Exa mples of conversion of the classes of ions to the Equ ivalent Neutral Class

Compound Molecular ion Rearrange Rule applied Equiv.Neutr

al
Class
E.N.C.
[Co(NH3)6]3+ [ML 6]3+ [ML 3(L+)3] L+ = X ML3X3

[CoF6]3- [MX6]3- [MX3(X-)3] X- = L ML3X3

[Co(NH3)4Cl2]+ [ML 4X2]+ [ML 3(L+)X2] L+ = X ML3X3

[Mn(CO)5]- [ML 5]- [ML 4(L-)] L- = LX ML5X

[Mn(CO)6]+ [ML 6]+ [ML 5(L+)] L+ = X ML5X

[Co(-C5H5)2]+ [ML 4X2]+ [ML 3(L+)X2] L+ = X ML3X3

[NiCl4]2- [MX4]2- [MX2(X-)2] X- = L ML2X2

[Pt(NH3)Cl3]- [MLX3]- [MLX2(X-)] X- = L ML2X2

[Cr(CO)5]2- [ML 5]2- [ML 3(L-)2] L- = LX ML5X2

[Ir(PR3)2H6]+ [ML 2X6]+ [ML(L+)X5 L+ = X MLX 7

NH4+ [ML 4]+ [MX3(X+)] X+ = Z ML3Z

PCl4+ [ML 4]+ [MX3(X+)] X+ = Z ML3Z

Counting electrons in a molecule MX L Zz
x l
Determination of Electron Number ( E,N.)

(1) Identify all the bonds in their appropriate

class. E.G. as X , L , Z, LX, Ll X , LXZ, etc
x l x

(2) Identify the number of valency electrons

in the central atom M. this ie denoted as Me.

(c) Calciulate the Electron Number from

E.N. = Me + 2L +X.
 Bonding in H
2
*
1s 1s


H + H +
 *
 Cy3
O P
C
H H
OC Mo Mo
H
C H
P O
Cy 3
Kubas
anti-bonding
_ + H
+ _+ +
+ Mo +
+
+ +
+ bonding H

two-electron three-centred bond

THE CLASSICAL EXAMPLE OF THE
THREE-ELECTRON BOND

H
H H
B B
H H
 The Half-arrow convention
Hydrogen acting as a H- L 3-electron ligand

H
H H
B B
H H

H
H .. H
B
B ..
H H
another way to raw it
How do you count electrons
in diborane?

6H = 6
H H H 2B = 6
B B
12
H H H
6 each?

6H = 6
H H 2C = 8
H C C H
H H 14
7 each?
Two-electron Three-centre Bonds in Metal-ligand Systems

Anti-bonding _
H
Non-bonding
+ M + +
+ + Bonding _ H
+
The 2e-3c bond of the transition
The 2-electron 3-centre bond metal-dihydrogen system.
(written as a 2e-3c bond)
Written as M( 2-H2)
of the H3+ cation. Alternatve VB drawings
A VB representation
H H H
+ M or M
H
H H H
back-donation
z
+
_ _ _
+ C
C
+ M + + + + M + + +
x
_ C + _ _ C
_
Showing the the
Showing both the forward
L-function (donor) donation AND the "back-donation ".
of the ethene ligand The back-donation is from the electron
in the metal-ethene bond. pair in the filled dzx metal orbital
Also known as into the empty p*-orbital of the ethene/
"forward donation " Known as the Chatt-Dewar model.
There is no simple black line VB
representation for this bonding.
C The ethene is described as a -acid -
M because it accepts an electron pair into
an empty orbital of-symmetry wrt to
C the M -ethene axis.
This back-donation and is called a
A common VB
representation d p bond .
( -C2H4)
Written as M 
 The agostic M-H-C bond

M C

half arrow H
convention
M C

An unsymmetrical two-electron, three-centre bond

formed between a C-H bond and a metal

 Classif icat ion of Al2 Me6
using t he half -arrow not at ion

H
H H
C
Me Me
B B
Me C Me
H H
H

Each Al has class MLX3 so EN = 8

 Me

Me
C
C
O O O O

Mo ? Mo

O C
H O
H H
C

Me
Mo 6 6

Cp 5 5

OAc 4 5

Me 2 1
17 17

Theref ore t o achieve t he 1 8 elect rons

a single bond is r equired.
 Classification of Covalent
Compounds of All the Elements

This requires the determination of

A. The Valency Number m denoted V.N.

B. The Ligand Bond Number, denoted L.B.N.

C. The Elecron Number, denoted E.N.

 DEFIN I TIONS

I Valency Number (V.N.) = x

(where x is the number of X-functions on the ligands) .

II Ligand Bond Number (L.B.N.) = l + x

(this is the sum of the number of L- and X-functions).

III Electro n Number (E.N.) = Me + 2l + x

Me is the number of electrons in the valency shell of the

element M.

The magnitude of the number n of dn is given as,

n = Me - x (-2z, where appropriate).

 ELEC TRO N NUMBER E.N.
12 13 14 15 16 17 18
ML 3 ML 4 ML 5 ML 6
0

ML 3 X ML 4 X ML 5 X
V 1
A
L
E ML 2 X 2 ML 3 X 2 ML 4 X 2 ML 5 X 2
N 2
C
Y
ML 2 X 3 ML 3 X 3 ML 4 X 3
N 3
U
M
B MLX 4 ML 2 X 4 ML 3 X 4 ML 4 X 4
E 4
R
V. MLX 5 ML 2 X 5 ML 3 X 5
N. 5

MX 6 MLX 6 ML 2 X 6 ML 3 X 6
6
 E LECTRON N UMBER , E.N.
12 13 14 15 16 17 18
V MoL 3 MoL 4 MoL 5 MoL 6
A
L 0
E
N
C MoL 3 X MoL 4 X MoL 5 X
Y 1

N
U MoL 2 X 2 MoL 3 X 2 MoL 4 X 2 MoL 5 X 2
M 2
B
E
R MoL 2 X 3 MoL 3 X 3 MoL 4 X 3
3

V.
N. MoLX 4 MoL 2 X 4 MoL 3 X 4 MoL 4 X 4
4

MoLX 5 MoL 2 X 5 MoL 3 X 5

5

MoX 6 MoLX 6 MoL 2 X 6 MoL 3 X 6

6

Increasing colour intensity

white
0 1-5 5-15 15-30 30-50 50-100 100-200 200-400

Increasing numbers of compounds in each class

Figu re 1. The MLX plot for molybdenum. The population den sity for each MLlXx class
is shown by the colour intensity scale
St abilit y of a Compound t owards
isolat ion at room t emperat ure
DO NOT CONFUSE

COORDINATION NUMBER C.N.

WITH LIGAND BOND NUMBER

FOR EXAMPLE

Ferrocene is class FeL 4 X2 so has L.B.N = 6

However t he coordinat ion number

C.N. of f errocene is 1 0 -- t here are
1 0 carbons bonding t o t he iron cent er
 1 Electron Number E.N.
12 13 14 15 16 17 18
V
MoL3 MoL4 MoL5 MoL6
a 0
l
e
n . MoL3X MoL4X MoL5X
c 1
y

N MoL2X 2 MoL3X2 MoL4X 2 MoL5X2

u 2
m
b
MoL2X 3 MoL3X 3 MoL4X 3
e
r 3

V. MoL2X4 MoL3X 4 MoL4X 4

N. 4 L.B.N = 5

MoLX 5 MoL2X5 MoL3X5

5

MoX 6 MoLX 6 MoL2X 6 MoL3X 6

6

L.B.N. = 6 L.B.N. = 7 L.B.N = 8 L.B.N. = 9

Figure 6.
V.N. 13 14 17 E.N
12 15 16 18
MoL3 MoL4 MoL5 MoL6
0
REGION OF -ACCEPTOR
. LIGANDS
MoL3X MoL4X
1 I
MoL3X2 MoL4X2 MoL5X2
22 BULKY LIGANDS
MoL2X2 REGION
MoL3X3 MoL4X3
3 V MEDIAN LIGANDS II
MoL1X4 MoL2X4 MoL3X4 MoL4X4
4

MoLX5 MoL2X5 MoL3X5

5

MoX6 MoL3 X6
MoLX MoL3X6
REGION FOR S TRONG -BONDS REGION OF HIGH L.B.N.
6 6
E.g. O, F, OR, NR2, H, Cl III S MALL LIGANDS ONLY IV
MLX Classification of Reactions according to Products ( no mechanism implied)

MoLl+1Xx-2
Reductive- Reductive-
elimination Replacement- replacement
elimination
MoLlXx-2 MoLl+2Xx-2
-X +L,-X

MoLlXx-1 +L,-2X MoLl+1Xx-1

-X +L,-X

L-elimination -L MoLlXx +L L-addition

MoLl-1Xx MoLl+1Xx

-L,+X +X

MoLl-1Xx+1 -L,+2X MoLlXx+1

-L,+X +X
Oxidative- Replacement- Oxidative-
replacement addition addition
MoLl-2Xx+2 MoLl-1Xx+2 MoLlXx+2
 Table 4. Classification of reactions by the reaction products

Change in Ll and/or Xx Change in Name of reaction

E.N. V.N.
-Ll then +L'l 0 0 Ll -substitution
-Xx then +X'x 0 0 Xx -substitution
+Ll +2l 0 Ll-addition
-Ll -2l 0 Ll-elimination
+Xx +x +x Xx-oxidative-addition
-Xx -x -x Xx-reductive-elimination
+L then -Xa +1 -1 reductive-replacementa
-L then +Xb -1 -1 oxidative-replacementb
-Ln then +X2n (n=1) 0 +2 replacement-additionc
+Ln then -X2n (n=1) 0 -2 replacement-eliminationd

L goes to new L' or 0 0 L-substitution

X goes to new X' 0 0 X-substitution

a When the ligand s are unchanged the reaction is a 1-electron reduction.

b When the ligand s are unchanged the reaction is a 1-electron oxid ation.
c Assuming n = 1. G enerally called n-replacement-addition.
d Assuming n = 1. G enerally called n-replacement-elimination.
 Partial charge on M
P o s it iv e Normal range Ne g a t iv e

+1 +0.5 0 -0.5 -1

MX F NH 3
ML

CO

M X2 F2 O (NH 3)2 M L2

C 6H6 M L3
M X3 F3 (CO) 3 (NH 3)3

M X4 F4 O H4
(PR 3)4 (NH 3)4 M L4
O2

M X5 F5 (P(OR) 3)5 (NH 3)5 M L5

M X6 M L6
M F6 M O3 M H6 M (P (OR) 3 ) 6 M (P R 3 ) 6 M (NH3 ) 6

M (CO) 6 M (C6 H6 )(CO) 3 M (C6 H6 ) 2

Figure 7
 LBN below 6 odd electron 18-electron rule -acid ligand
very rare, e.g. molecules very well observed region, e.g. CO, benzene
M oCl5 vapour are rare

Molybdenum E lectron Num ber, E . N.

Diagonal group- 12 13 14 15 16 17 18

electron transfer- V
a 0
MoL 3 MoL 4 MoL 5 MoL 6

redox activity l
e LBN = 7,
n
-Cp lignds
MoL 3 X MoL 4 X MoL 5 X
c
1
y
N
u
MoL 2 X 2 MoL 3 X 2 MoL 4 X 2 MoL 5 X 2 common
m 2
b
maximum VN e
r 3
MoL 2 X 3 MoL 3 X 3 MoL 4 X 3
+X2 reaction,
well populated
- reflects M o is
V.
N.
4
MoL X 4 MoL 2 X 4 MoL 3 X 4 MoL 4 X 4 e.g. molybdenocene
relatively electro MoL 2 X 5 MoL 3 X 5
positive and lower 5
MoL X 5

sensitivity of MoX 6 MoL X 6 MoL 2 X 6 MoL 3 X 6

4d shell 6

LBN = 6 is horizontal
well favoured group interrelated both grouping- shows LBN = 9 (steric saturation probable
by redox (diagonal) and L-ligand lability hence - typically compact ligands
substitutional (horizontal) required -as in [M o(NH3)3O3] and
[M oO4]+ and M oO3 populations - this gives rise to
not oxidising, even a rich complex chemistry- [M o(-Cp)2H 3]+
especially with aqueous ligand
in strong H + systems
 18-electron rule
Comments on Cr, VN = 3, d 3 very well obeyed as the
Remarkable non-lability,
CHROMIUM inert to substitution,
3d , 4s and 4p orbitals
all have "valency energy"
but as diagonal relationship
shows, s readily reduced

Chromium Electron Number, E.N.

12 13 14 15 16 17 18
LBN = 6 very well V
a 0
CrL 3 CrL 4 CrL 5 CrL 6 Compounds in
represented. Higher l
e this region are very
values of LBN are
n CrL 2 X
similar to those of
CrL 3 X CrL 4 X CrL 5 X
c
1
y
most often found N CrL 2 X 2 CrL 3 X 2 CrL 4 X 2 CrL 5 X 2 M o and W
when EN = 18. u
m
2
b
e CrL 2 X 3 CrL 3 X 3 CrL 4 X 3
r CrLX 3
3
L-substitution by
V.
N. 4
CrLX 4 CrL 2 X 4 CrL 3 X 4 CrL 4 X 4 dissciative mechanism
CrX 5 CrLX 5 CrL 2 X 5 CrL 3 X 5
L-substitution by
5

6
CrX 6 CrLX 6 CrL 2 X 6 CrL 3 X 6 associative mechanism

K2CrO4 and CrO 3 are

This region is very different
from M o and W: the higher VN strongly oxidising in H + acid. The absence of both CrL 2 X3
region is much less populated and CrL 4 X3 - for which LBN = 5
for Cr- due to the sensitivity
of 3d orbitals to induced charge and 7, respectively, clearly
AND the ligand orbitals required reflects of the L-substitutional
for desired strong -bonds are those inertness of CrL 3 X3
(2p) of C,N,O and F, which are
the relatively electronegatve.atoms.
Electron energies in 3d orbitals are
more sensitive to charge-
compared to 4d and 5d
 LBN = 4 common
18-electon rule quite
since already d 10, gives well obeyed, except that
NiL4. Also, 16-electron d8 NiL2X 2 very common and
electronically favoured 20e NiL 4X 2 also found Tetrahedral, d10 NiL4
has weakish M-L bonds
M LX plots for Nickel, Palladium and Platinum since the d-electrons are
A few examples of Nickel Electron Number E.N. low in energy. Ligand
VN = 1, reflecting 12 13 14 15 16 17 18 19 20 dissociation (-L) a common
V
steric saturation, a 0 NiL
NiL2 NiL3 NiL4 NiL5
reaction step.
e.g. [Ni(PPh 3)3]+
l
e
n NiX NiLX NiL2X NiL3X NiL4X
c 1
y Rare examples of
L-substitution by N 2 NiX2
NiLX2 NiL2X2 NiL3X2 NiL4X2 20-electron compounds
(i) Associative mechanism
u
m
but note LBN = 6.
(ii) Both (i) and (iii) b
e 3
NiX3 NiLX3 NiL2X3 NiL3X3

(iii) Dissociative mechanism r

V. 4 NiX4 NiLX4 NiL2X4 NiL3X4

Shows LBN = 6 favoured N. Higher VN = 3 or 4 are

NiX5 NiLX5 NiL2X5
very rare since Ni has 3d
Simple redox chemistry is 5 orbitals and high I.P's, as
rare for Ni and virtually NiX6 NiLX6 NiL2X6
expected towards end of
unknown for Pd and Pt. 6 d-block.
This reflected by absence
of diagonal groups. Palladium Electron Number E.N.
i.e. absence of odd-electron V
12 13
PdL2
14 15
PdL3
16 17
PdL4
18 19
PdL5
20
L-substitution by
PdL
compounds. a 0
dissociative process
l
e
n PdX PdLX PdL2X PdL3X PdL4X
c 1
y L-substitution by
The special case of PdX2 PdLX2 PdL2X2 PdL3X2 PdL4X2 associative process
N2
d8 configuration. u
m
No Td structures as b PdX3 PdLX3 PdL2X3 PdL3X3
e 3
Td inceases r Related by +/-X2.
PdX4 PdLX4 PdL2X4 PdL3X4
V. 4
N.
Oxidative-addition/
PdX5 PdLX5 PdL2X5
reductive elimination
5 reactions are very
common
PdX6 PdLX6 PdL2X6
Increasing stabilisation 6

of higher VN
Platinum Electron Number E.N.
12 13 14 15 16 17 18 19 20
V
a 0 PtL PtL2 PtL3 PtL4 PtL5
l
e Related by +/-X2.
n PtX PtLX PtL2X PtL3X PtL4X
c 1 Oxidative-addition/
y
reductive elimination
NO odd electron N 2 PtX2 PtLX2 PtL2X2 PtL3X2 PtL4X2
reactions are very
compounds known u
m common
b PtX3 PtLX3 PtL2X3 PtL3X3
e 3
r
V. PtX4 PtLX4 PtL2X4 PtL3X4
N.4

NO 20-electron PtX5 PtLX5 PtL2X5

compounds known, 5

for Pd and Pt. This LBN = 6

PtX6 PtLX6 PtL2X6
reflects increase in 6

Oh
Increasing stabilisation
of higher VN. e.g. PtF 6
 Platinum Electron Number E.N.
12 13 14 15 16 17 18 19 20
V PtL2 PtL3 PtL4 PtL5
a 0 PtL
l
e
n PtX PtLX PtL2X PtL3X PtL4X
c 1
y
PtLX2 PtL2X2 PtL3X 2 PtL4X2
N 2 PtX2
u
m
b PtX3 PtLX3 PtL2X 3 PtL3X 3
e 3
r

V. 4 PtX4 PtLX4 PtL2X4 PtL3X4

N.
PtX5 PtLX5 PtL2X 5
5

PtX6 PtLX6 PtL2X6

6
 C HROMIUM E LECTRON N UMBER , E.N.
12 13 14 15 16 17 18
CrL 3 CrL 4 CrL 5 CrL 6
V 0
A
L CrL 3 X CrL 4 X CrL 5 X
E 1
N
C CrL 2 X 2 CrL 3 X 2 CrL 4 X 2 CrL 5 X 2
Y 2

N CrL 2 X 3 CrL 3 X 3 CrL 4 X 3

3
U
M
B CrLX 4 CrL 2 X 4 CrL 3 X 4 CrL 4 X 4
4
E
R CrLX 5 CrL 2 X 5 CrL 3 X 5
5

V. CrX CrLX 6 CrL 2 X 6 CrL 3 X 6

6 6
N.

M OLYBDENUM E LECTRON N UMBER , E.N.

12 13 14 15 16 17 18
MoL 3 MoL 4 MoL 5 MoL 6
V 0
A
L MoL 3 X MoL 4 X MoL 5 X
E 1
N
C MoL 2 X 2 MoL 3 X 2 MoL 4 X 2 MoL 5 X 2
Y 2

N MoL 2 X 3 MoL 3 X 3 MoL 4 X 3

3
U
M
B MoLX 4 MoL 2 X 4 MoL 3 X 4 MoL 4 X 4
4
E
R MoLX MoL 2 X 5 MoL 3 X 5
5 5

V. MoX MoLX MoL 2 X 6 MoL 3 X 6

6 6
N. 6

T UNGSTEN E LECTRON N UMBER , E.N.

12 13 14 15 16 17 18
V WL 3 WL 4 WL 5 WL 6
A 0
L
E WL 3 X WL 4 X WL 5 X
1
N
C WL 5 X 2
Y WL 2 X 2 WL 3 X 2 WL 4 X 2
2

N
WL 2 X 3 WL 3 X 3 WL 4 X 3
U 3
M
B WLX 4 WL 2 X 4 WL 3 X 4 WL 4 X 4
E 4
R
WLX 5 WL 2 X 5 WL 3 X 5
5
V.
N. WX 6 WLX 6 WL 2 X 6 WL 3 X 6
6

Figure 10
 MLX plots for Titanium, Zirconium and Hafnium
T itanium Electron Number E.N.
V 8 9 10 11 12 13 14 15 16 17 18
a T iL2 T iL3 T iL4 T iL5 T iL6 T iL7
l 0
e
n
T iLX T iL2 X T iL3 X T iL4 X T iL5 X T iL6 X
c
y 1
N T iLX 2 T iL2 X 2 T iL3 X 2 T iL4 X 2 T iL5 X 2 T iL6 X 2
u 2
m
b
e T iX3 T iLX 3 T iL2 X 3 T iL3 X 3 T iL4 X 3 T iL5 X 3
r 3
V. T iX4 T iLX 4 T iL2 X 4 T iL3 X 4 T iL4 X 4 T iL5 X 4
N. 4

Zirconium Electron Number E.N.

V 8 9 10 11 12 13 14 15 16 17 18
a ZrL 2 ZrL 3 ZrL 4 ZrL 5 ZrL 6 ZrL 7
l 0
e
n
ZrLX ZrL 2 X ZrL 3 X ZrL 4 X ZrL 5 X ZrL 6 X
c
y 1
N ZrLX 2 ZrL 2 X 2 ZrL 3 X 2 ZrL 4 X 2 ZrL 5 X 2 ZrL 6 X 2
u 2
m
b
e ZrX 3 ZrLX 3 ZrL 2 X 3 ZrL 3 X 3 ZrL 4 X 3 ZrL 5 X 3
r 3
V. ZrX 4 ZrLX 4 ZrL 2 X 4 ZrL 3 X 4 ZrL 4 X 4 ZrL 5 X 4
N. 4

Hafnium Electron Number E.N.

V 8 9 10 11 12 13 14 15 16 17 18
a HfL 2 HfL 3 HfL 4 HfL 5 HfL 6 HfL 7
l 0
e
n
HfLX HfL 2 X HfL 3 X HfL 4 X HfL 5 X HfL 6 X
c
y 1
N HfLX 2 HfL 2 X 2 HfL 3 X 2 HfL 4 X 2 HfL 5 X 2 HfL 6 X 2
u 2
m
b
e HfX 3 HfLX 3 HfL 2 X 3 HfL 3 X 3 HfL 4 X 3 HfL 5 X 3
r 3
V. HfX 4 HfLX 4 HfL 2 X 4 HfL 3 X 4 HfL 4 X 4 HfL 5 X 4
N. 4
 The MLX plot for nickel. ELECTRON NUMBER E.N.
V 14 15 16 17 18 19 20
A NiL NiL3 NiL4 NiL5
0 2
L
E NiL2X NiL3X NiL4X
1
N
C NiL3X2 NiL4X2
2 NiLX2 NiL2X2
Y

3 NiLX3 NiL2X3 NiL3X3

N
U
4 NiX4 NiLX4 NiL2X4 NiL3X4
M
B
NiX5 NiLX5 NiL2X5
E 5
R
V. 6 NiX6 NiLX6 NiL2X6
N.
The MLX plot for palladium. ELECTRON NUMBER E.N.
14 15 16 17 18 19 20
V
A 0 PdL 2 PdL3 PdL4 PdL5
L
E 1 . PdL2X PdL3X PdL4X
N
C PdL2X2
2 PdLX2 PdL3X2 PdL4X2
Y
PdLX3 PdL2X3 PdL3X3
N 3
U PdL3X4
PdX4 PdLX4 PdL2X4
M 4
B
E PdX5 PdLX5 PdL2X5
5
R
V. PdX6 PdLX6 PdL2X6
6
N. The MLX plot for platinum. ELECTRON NUMBER E.N.
The MLX plot for platinum. ELECTRON NUMBER E.N.
14 15 16 17 18 19 20
V
A 0 PtL2 PtL3 PtL4 PtL5
L
E . PtL2X PtL3X PtL4X
1
N
C PtL2X2 PtL3X2 PtL4X2
PtLX2
Y 2

3 PtLX3 PtL2X3 PtL3X3

N
U
M 4 PtX4 PtLX4 PtL2X4 PtL3X4
B
E PtX5 PtLX5 PtL2X5
5
R
V. PtX6 PtLX6 PtL2X6
6
N.
 MLX plots for Vanadium, Niobium and Tantalum

Vanadium
Electron Number E.N.
11 12 13 14 15 16 17 18 19
V VL 4 VL 5 VL 6 VL 7
a VL 3
0
l
e
n VL 2 X VL 3 X VL 4 X VL 5 X VL 6 X
c 1
y

N VL 2 X 2 VL 3 X 2 VL 4 X 2 VL 5 X 2 VL 6 X 2
2
u
m
b VLX 3 VL 2 X 3 VL 3 X 3 VL 4 X 3 VL 5 X 3
e 3
r

V. VLX 4 VL 2 X 4 VL 3 X 4 VL 4 X 4 VL 5 X 4
4
N.

VX 5 VLX 5 VL 2 X 5 VL 3 X 5 VL 4 X 5
5

Niobium Electron Number E.N.

11 12 13 14 15 16 17 18 19
V NbL 4 NbL 5 NbL 6 NbL 7
a NbL 3
0
l
e
n NbL 2 X NbL 3 X NbL 4 X NbL 5 X NbL 6 X
c 1
y

N NbL 2 X 2 NbL 3 X 2 NbL 4 X 2 NbL 5 X 2 NbL 6 X 2

2
u
m
b NbLX 3 NbL 2 X 3 NbL 3 X 3 NbL 4 X 3 NbL 5 X 3
e 3
r
V.
N. NbLX 4 NbL 2 X 4 NbL 3 X 4 NbL 4 X 4 NbL 5 X 4
4

NbX 5 NbLX 5 NbL 2 X 5 NbL 3 X 5 NbL 4 X 5

5

Tantalum Electron Number E.N.

11 12 13 14 15 16 17 18 19
V TaL 4 TaL 5 TaL 6 TaL 7
a TaL 3
0
l
e
n TaL 2 X TaL 3 X TaL 4 X TaL 5 X TaL 6 X
c 1
y

N TaL 2 X 2 TaL 3 X 2 TaL 4 X 2 TaL 5 X 2 TaL 6 X 2

2
u
m
b TaLX 3 TaL 2 X 3 TaL 3 X 3 TaL 4 X 3 TaL 5 X 3
e 3
r
V.
N. TaLX 4 TaL 2 X 4 TaL 3 X 4 TaL 4 X 4 TaL 5 X 4
4

TaX 5 TaLX 5 TaL 2 X 5 TaL 3 X 5 TaL 4 X 5

5
 MLX Plots for Chromium, Molybdenum and Tungsten
Chromium
Electron Number, E.N.
12 13 14 15 16 17 18
V CrL 3 CrL 4 CrL 5 CrL 6
a 0
l
e CrL 3 X CrL 4 X CrL 5 X
n 1
c
CrL 2 X 2 CrL 3 X 2 CrL 4 X 2 CrL 5 X 2
y 2

N CrL 2 X 3 CrL 3 X 3 CrL 4 X 3

u 3
m
b CrLX 4 CrL 2 X 4 CrL 3 X 4 CrL 4 X 4
e 4
r
CrLX 5 CrL 2 X 5 CrL 3 X 5
5
V.
N. CrX CrLX 6 CrL 2 X 6 CrL 3 X 6
6 6

Molybdenum
Electron Number, E.N.
12 13 14 15 16 17 18
V MoL 3 MoL 4 MoL 5 MoL 6
a 0
l
e MoL 3 X MoL 4 X MoL 5 X
n 1
c
y MoL 2 X 2 MoL 3 X 2 MoL 4 X 2 MoL 5 X 2
2
N
MoL 2 X 3 MoL 3 X 3 MoL 4 X 3
u 3
m
b MoLX MoL 2 X 4 MoL 3 X 4 MoL 4 X 4
e 4 4
r
MoLX MoL 2 X 5 MoL 3 X 5
5 5
V.
N. MoX MoLX 6 MoL 2 X 6 MoL 3 X 6
6 6

Tungsten
Electron Number, E.N.
12 13 14 15 16 17 18
V WL 3 WL 4 WL 5 WL 6
a 0
l
e WL 3 X WL 4 X WL 5 X
n 1
c WL 5 X 2
WL 2 X 2 WL 3 X 2 WL 4 X 2
y 2
N
WL 2 X 3 WL 3 X 3 WL 4 X 3
u 3
m
b WLX 4 WL 2 X 4 WL 3 X 4 WL 4 X 4
e 4
r
WLX 5 WL 2 X 5 WL 3 X 5
5
V.
N. WX 6 WLX 6 WL 2 X 6 WL 3 X 6
6
 MLX plots for Manganese, Technetium and Rhenium
M anganese Electron Number E.N.
11 12 13 14 15 16 17 18 19
MnL 2 MnL 3 MnL 4 MnL 5 MnL 6
0
V
a
l MnL 2 X MnL 3 X MnL 4 X MnL 5 X
e 1
n
c 2 MnLX 2 MnL 2 X 2 MnL 3 X 2 MnL 4 X 2 MnL 5 X 2
y
N MnLX 3 MnL 2 X 3 MnL 3 X 3 MnL 4 X 3
u 3
m
b 4 MnX 4 MnLX 4 MnL 2 X 4 MnL 3 X 4 MnL 4 X 4
e
r
MnX 5 MnLX 5 MnL 2 X 5 MnL 3 X 5
V. 5
N.
MnX 6 MnLX 6 MnL 2 X 6 MnL 3 X 6
6

MnX 7 MnLX 7 MnL 2 X 7

7

Technetium Electron Number E.N.

11 12 13 14 15 16 17 18 19

TcL 2 TcL 3 TcL 4 TcL 5 TcL 6

0
V
a
l TcL 2 X TcL 3 X TcL 4 X TcL 5 X
e 1
n
c TcLX 2 TcL 2 X 2 TcL 3 X 2 TcL 4 X 2 TcL 5 X 2
2
y
N TcLX 3 TcL 2 X 3 TcL 3 X 3 TcL 4 X 3
3
u
m
b TcX 4 TcLX 4 TcL 2 X 4 TcL 3 X 4 TcL 4 X 4
4
e
r
TcX 5 TcLX 5 TcL 2 X 5 TcL 3 X 5
5
V.
N.
TcX 6 TcLX 6 TcL 2 X 6 TcL 3 X 6
6

7 TcX 7 TcLX 7 TcL 2 X 7

Rhenium Electron Number E.N.

11 12 13 14 15 16 17 18 19
ReL 2 ReL 3 ReL 4 ReL 5 ReL 6
0
V
a
l ReL 2 X ReL 3 X ReL 4 X ReL 5 X
e 1
n
c ReLX 2 ReL 2 X 2 ReL 3 X 2 ReL 4 X 2 ReL 5 X 2
2
y

N ReLX 3 ReL 2 X 3 ReL 3 X 3 ReL 4 X 3

u 3
m
b ReX 4 ReLX 4 ReL 2 X 4 ReL 3 X 4 ReL 4 X 4
4
e
r
ReX 5 ReLX 5 ReL 2 X 5 ReL 3 X 5
5
V.
N.
ReX 6 ReLX 6 ReL 2 X 6 ReL 3 X 6
6

7 ReX 7 ReLX 7 ReL 2 X 7

 MLX plots for Iron, Ruthenium and Osmium
Iron Electron Number E.N.
10 11 12 13 14 15 16 17 18
V FeL FeL 2 FeL 3 FeL 4 FeL 5
a 0

l
e FeX FeLX FeL 2 X FeL 3 X FeL 4 X
1
n
c
FeX 2 FeLX 2 FeL 2 X 2 FeL 3 X 2 FeL 4 X 2
y 2

N FeX 3 FeLX FeL 2 X 3 FeL 3 X 3

u 3
3
m
b FeX 4 FeLX FeL 2 X 4 FeL 3 X 4
4
e 4
r
FeX 5 FeLX FeL 2 X 5
V. 5 5
N'
FeX 6 FeLX 6 FeL 2 X 6
6

7 FeX 7 FeLX 7
8 FeX 8 FeLX 8

Ruthenium Electron Number E.N.

10 11 12 13 14 15 16 17 18
V RuL RuL 2 RuL 3 RuL 4 RuL 5
0
a
l
e RuX RuLX RuL 2 X RuL 3 X RuL 4 X
n 1
c
RuX RuLX 2 RuL 2 X 2 RuL 3 X 2 RuL 4 X 2
y 2 2

N RuX RuLX RuL 2 X 3 RuL 3 X 3

u 3 3
3
m
b RuX RuLX RuL 2 X 4 RuL 3 X 4
4 4
e 4
r
RuX 5 RuLX RuL 2 X 5
5
V. 5
N'
RuX 6 RuLX 6 RuL 2 X 6
6

7 RuX 7 RuLX 7
8 RuX 8 RuLX 8

Osmium Electron Number E.N.

10 11 12 13 14 15 16 17 18
V OsL OsL 2 OsL 3 OsL 4 OsL 5
a 0
l
e OsX OsLX OsL 2 X OsL 3 X OsL 4 X
n 1
c
OsX 2 OsLX 2 OsL 2 X 2 OsL 3 X 2 OsL 4 X 2
y 2

N OsX 3 OsLX OsL 2 X 3 OsL 3 X 3

u 3
3
m
b OsX 4 OsLX OsL 2 X 4 OsL 3 X 4
4
e 4
r
OsX 5 OsLX OsL 2 X 5
5
V. 5
N'
OsX 6 OsLX 6 OsL 2 X 6
6

7 OsX 7 OsLX 7
8 OsX 8 OsLX 8
 MLX plots for Cobalt, Rhodium and Iridium
Cobalt Electron Num ber E.N .
11 12 13 14 15 16 17 18 19
V CoL 2 CoL 3 CoL 4 CoL 5
a 0
CoL
l
e
n CoLX CoL 2 X CoL 3 X CoL 4 X
c 1
y
CoX 2 CoLX 2 CoL 2 X 2 CoL 3 X 2 CoL 4 X 2
N 2
u
m
b CoX 3 CoLX 3 CoL 2 X 3 CoL 3 X 3
e 3
r

V. 4 CoX 4 CoLX 4 CoL 2 X 4 CoL 3 X 4

N.
CoX 5 CoLX 5 CoL 2 X 5
5

CoX 6 CoLX 6 CoL 2 X 6

6

Rhodium Electron Num ber E.N .

11 12 13 14 15 16 17 18 19
V RhL 2 RhL 3 RhL 4 RhL 5
a 0
RhL
l
e
n RhLX RhL 2 X RhL 3 X RhL 4 X
c 1
y
RhX 2 RhLX 2 RhL 2 X 2 RhL 3 X 2 RhL 4 X 2
N 2
u
m
b RhX 3 RhLX 3 RhL 2 X 3 RhL 3 X 3
e 3
r
V. RhX 4 RhLX 4 RhL 2 X 4 RhL 3 X 4
4
N.
RhX 5 RhLX 5 RhL 2 X 5
5

RhX 6 RhLX 6 RhL 2 X 6

6

Iridium Electron Number E.N.

11 12 13 14 15 16 17 18 19
V IrL IrL 2 IrL 3 IrL 4 IrL 5
a 0
l
e
n IrLX IrL 2 X IrL 3 X IrL 4 X
c 1
y
IrX 2 IrLX 2 IrL 2 X 2 IrL 3 X 2 IrL 4 X 2
N 2
u
m
b IrX 3 IrLX 3 IrL 2 X 3 IrL 3 X 3
e 3
r
IrX 4 IrLX 4 IrL 2 X 4 IrL 3 X 4
V. 4
N.

IrX 5 IrLX 5 IrL 2 X 5

5

IrX 6 IrLX 6 IrL 2 X 6

6
7 Ir(PR 3 )H 7
 MLX plots for Nickel, Palladium and Platinum
Nickel Electron Number E.N.
12 13 14 15 16 17 18 19 20
V NiL NiL 2 NiL 3 NiL 4 NiL 5
a 0
l
e
n NiX NiLX NiL 2 X NiL 3 X NiL 4 X
c 1
y
NiX 2 NiLX 2 NiL 2 X 2 NiL 3 X 2 NiL 4 X 2
N 2
u
m
b NiX 3 NiLX 3 NiL 2 X 3 NiL 3 X 3
e 3
r
NiX 4 NiLX 4 NiL 2 X 4 NiL 3 X 4
V. 4
N.

NiX 5 NiLX 5 NiL 2 X 5

5

NiX 6 NiLX 6 NiL 2 X 6

6

Palladium Electron Number E.N.

12 13 14 15 16 17 18 19 20
V P dL P dL 2 P dL 3 P dL 4 P dL 5
a 0
l
e
n P dX P dLX P dL 2 X P dL 3 X P dL 4 X
c 1
y
P dX 2 P dLX 2 P dL 2 X 2 P dL 3 X 2 P dL 4 X 2
N 2
u
m
b P dX 3 P dLX 3 P dL 2 X 3 P dL 3 X 3
e 3
r

V. P dX 4 P dLX 4 P dL 2 X 4 P dL 3 X 4
4
N.
P dX 5 P dLX 5 P dL 2 X 5
5

P dX 6 P dLX 6 P dL 2 X 6
6

Platinum Electron Number E.N.

12 13 14 15 16 17 18 19 20
V
a P tL P tL 2 P tL 3 P tL 4 P tL 5
0
l
e
n P tX P tLX P tL 2 X P tL 3 X P tL 4 X
c 1
y

N P tX 2 P tLX 2 P tL 2 X 2 P tL 3 X 2 P tL 4 X 2
2
u
m
b P tX 3 P tLX 3 P tL 2 X 3 P tL 3 X 3
e 3
r

V. P tX 4 P tLX 4 P tL 2 X 4 P tL 3 X 4
4
N.

P tX 5 P tLX 5 P tL 2 X 5
5

6
P tX 6 P tLX 6 P tL 2 X 6
 MLX plots for Titanium, Manganese and Nickel

M anganese Electron Number E.N.

Titanium Electron Number E.N. 11 Nickel Electro n Nu mb er E.N.
12 13 14 15 16 17 18 19
V 8 9 10 11 12 13 14 15 16 17 18 MnL 12 13 14 15 16 17 18 19 20
MnL
2 MnL
3 MnL
4 5 MnL
6 V NiL NiL NiL NiL NiL
a TiL
2 TiL
3 TiL
4 TiL
5 TiL
6 TiL
7 V0
a0
2 3 4 5
l 0 a l
e l MnL
2X MnL3X MnL
4X MnL5X e
n TiLXTiLX TiLX TiLX TiLX TiLX e1 n NiX NiLX NiL
2X NiL
3X NiL
4X
c 2 3 4 5 6 c1
n y
y1 c MnLX
2 MnL
2X2 MnL
3X2 MnL
4X2 MnL
5X2 NiX
2 NiLX
2 NiL
2X2 NiL
3X2 NiL
4X2
y2 N
N TiLX2 TiL
2X2 TiL
3X2 TiL
4X2 TiL
5X2 TiL6X2 u2
MnLX MnL m
u2 N 3 2X3 MnL3X3 MnL 4X3 b NiX NiLX NiL
m u3 3 3 2X3 NiL
3X3
e3
b m r
TiX
3 TiLX
3 TiL2X3 TiL
3X3 TiL
4X3 TiL
5X3
e b 4 MnX MnLX MnL
r3 4 4 2X4 MnL 3X4 MnL 4X4 V.
NiX
4 NiLX4 NiL
2X4 NiL
3X4
e N.4
r
V. TiX
4 TiLX
4 TiL
2X4 TiL
3X4 TiL
4X4 TiL
5X4 MnX
5 MnLX
5 MnL
2X5 MnL3X5 NiX NiLX NiL
N.4 5 5 2X5
V.5 5
N.
6
MnX
6 MnLX6 MnL
2X6 MnL 3X6 NiX
6 NiLX
6 NiL
2X6
6

7
MnX
7 MnLX
7 MnL
2X7

Rule 1) Filled orbitals (18 electrons): Only possible for Ti when there are very small or compact
ligands since a further 14-electrons are required. E.g. [TiCp 2(CO)2]. TiCl4 is apparently an
8-electron compound but if the symmetry allowed contributions from the Cl p -orbitals are counted
then there are an extra 10 electrons which gives the value for EN = 18-electrons!
For M n, excellent for VN = 1 where also LBN = 6. but poor for VN = 3 and 5 since
LNB = 7 or 8 respectively AND higher VN for M n are rare since 3d orbitals are rapidly lowered
in energy by the increasing patrial +ve change on the M n centre.
For Ni, 18-electrons are found for NiL 4, NiL3X2 and (very rare) NiL 2X4,. Higher VN's for Ni
not found since increase effective nuclear charge at this end of the d-block TM 's means the
I.P.'s too high. The special stability of square-planer, 16-electron NiL2X2 is associated with
the d8 configuration.

Rule 2) S teric saturation:For Ti: unusually high LBN's (and high co-ordination nos)
are commonly found, e.g. in 16-electron TiL 4X4, LBN = 8. For Ni. low LBN's (3,4,5) are found
since Ni already has 10 electrons and only requires 4 x L ligands to give 18e NiL 4 , e.g. Ni(CO) 4.

Rule 3) Electroneutrality rule:For Ti: since I.P.'s are low all 4 valency electrons are
accessible to most ligands, e.g TiI 4.
For M n, the increase of effective nuclear charge with increasing atomic number across the
d-block elements means that the higher VN's are only obtainable with the first row elements
as ligand atoms (since these for the strongest -bonds). Hence VN = 4 is found with F,
O, N, and C ligands, e.g. M nR 4, R = CH2SiM e3. VN = 7 is known only for [M n(=X)4]-, where
X = O or NR, the electron donation from the appropriate symmetry combination of the p=orbitals
of the X ligands and the negative charge resulting from the anion helps reduce the induced positive
charge on the M n centre. Nonetheless, the [M nO4]- and M n2O 7 compounds are amongst the most
oxidising known (in aqueous acid). which shows these M n centres have exceptionally high partial
+ve charges.
 Titanium Electron Number E.N.
V 8 9 10 11 12 13 14 15 16 17 18
a T iL2 T iL3 T iL4 T iL5 T iL6 T iL7
l 0
e
n
T iLX T iL2 X T iL3 X T iL4 X T iL5 X T iL6 X
c
y 1
N T iLX 2 T iL2 X 2 T iL3 X 2 T iL4 X 2 T iL5 X 2 T iL6 X 2
u 2
m
b
e T iX3 T iLX 3 T iL2 X 3 T iL3 X 3 T iL4 X 3 T iL5 X 3
r 3
V. T iX4 T iLX 4 T iL2 X 4 T iL3 X 4 T iL4 X 4 T iL5 X 4
N. 4
 Zirconium Electron Number E.N.
V 8 9 10 11 12 13 14 15 16 17 18
a ZrL2 ZrL3 ZrL4 ZrL5 ZrL6 ZrL7
l 0
e
n
ZrLX ZrL2X ZrL3X ZrL4X ZrL5X ZrL6X
c
y 1

N ZrLX2 ZrL2X2 ZrL3X2 ZrL4X2 ZrL5X2 ZrL6X2

u 2
m
b
e ZrX3 ZrLX3 ZrL2X3 ZrL3X3 ZrL4X3 ZrL5X3
r 3

V. ZrX4 ZrLX4 ZrL2X4 ZrL3X4 ZrL4X4 ZrL5X4

N. 4
 Hafnium Electron Number E.N.
V 8 9 10 11 12 13 14 15 16 17 18
a HfL2 HfL3 HfL4 HfL5 HfL6 HfL7
l 0
e
n HfLX HfL X HfL3X HfL4X HfL5X HfL6X
c 2
y 1

N HfLX2 HfL2X2 HfL3X2 HfL4X2 HfL5X2 HfL6X2

u 2
m
b
e HfX3 HfLX3 HfL2X3 HfL3X3 HfL4X3 HfL5X3
r 3

V. HfX4 HfLX4 HfL2X4 HfL3X4 HfL4X4 HfL5X4

N. 4
 Vanadium Electron Number E.N.
11 12 13 14 15 16 17 18 19
V VL 4 VL 5 VL 6 VL 7
VL 3
a 0
l
e
n VL 2X VL 3X VL 4X VL 5X VL 6X
c 1
y
VL 3X2 VL 4X2 VL 5X2 VL 6X2
N 2 VL 2X2
u
m
b VLX3 VL 2X3 VL 3X3 VL 4X3 VL 5X3
e 3
r
VLX4 VL 2X4 VL 3X4 VL 4X4 VL 5X4
V. 4
N.
VX5 VLX5 VL 2X5 VL 3X5 VL 4X5
5
 Niobium Electron Number E.N.
11 12 13 14 15 16 17 18 19
V NbL4 NbL5 NbL6 NbL7
NbL3
a 0
l
e
n NbL2X NbL3X NbL4X NbL5X NbL6X
c 1
y
NbL3X2 NbL4X2 NbL5X2 NbL6X2
N 2 NbL2X2
u
m
b NbLX3 NbL2X3 NbL3X3 NbL4X3 NbL5X3
e 3
r
V. NbLX4 NbL2X4 NbL5X4
N. 4 NbL3X4 NbL4X4

NbX5 NbLX5 NbL2X5 NbL3X5 NbL4X5

5
 Tantalum Electron Number E.N.
11 12 13 14 15 16 17 18 19
V TaL4 TaL5 TaL6 TaL7
TaL3
a 0
l
e
n TaL2X TaL3X TaL4X TaL5X TaL6X
c 1
y
TaL3X2 TaL4X2 TaL5X2 TaL6X2
N 2 TaL2X2
u
m
b TaLX3 TaL2X3 TaL3X3 TaL4X3 TaL5X3
e 3
r
V. TaLX4 TaL2X4 TaL5X4
N. 4 TaL3X4 TaL4X4

TaX5 TaLX5 TaL2X5 TaL3X5 TaL4X5

5
 Chromium Electron Number, E.N.
12 13 14 15 16 17 18
V CrL3 CrL4 CrL5 CrL6
a 0
l
e
n CrL2X CrL3X CrL4X CrL5X
c 1
y

N CrL2X 2 CrL3X 2 CrL4X 2 CrL5X 2

u 2
m
b
e CrLX3 CrL2X3 CrL3X 3 CrL4X 3
r 3

V. CrLX 4 CrL2X 4 CrL3X4 CrL4X 4

N.
4

CrX 5 CrLX 5 CrL2X 5 CrL3X 5

5

CrX 6 CrLX 6 CrL2X6 CrL3X 6

6
 Molybdenum Electron Number, E.N.
12 13 14 15 16 17 18
V M oL3 M oL4 M oL5 M oL6
a 0
l
e
n M oL3X M oL4X M oL5X
c 1
y

N M oL2X2 M oL3X 2 M oL4X 2 M oL5X 2

u 2
m
b
e M oL2X3 M oL3X 3 M oL4X 3
r 3

V. M oLX4 M oL2X 4 M oL3X 4 M oL4X 4

N.
4

M oLX5 M oL2X 5 M oL3X 5

5

M oX 6 M oLX6 M oL2X 6 M oL3X 6

6
 Tungsten Electron Number, E.N.
12 13 14 15 16 17 18
V WL 3 WL 4 WL 5 WL 6
a 0
l
e
n WL 3X WL 4X WL 5X
c 1
y

N WL 2X2 WL 3X 2 WL 4X 2 WL 5X 2
u 2
m
b
e WL 2X3 WL 3X 3 WL 4X 3
r 3

V. WLX 4 WL 2X 4 WL 3X4 WL 4X 4
N. 4

WLX5 WL 2X 5 WL 3X 5
5

WX 6 WLX6 WL 2X6 WL 3X 6
6
 M anganese Electron Number E.N.
11 12 13 14 15 16 17 18 19

M nL2 M nL3 M nL4 M nL5 M nL6

0
V
a
l M nL2X M nL3X M nL4X M nL5X
e 1
n
c 2
M nLX2 M nL2X 2 M nL3X 2 M nL4X2 M nL5X 2
y

N M nLX3 M nL2X3 M nL3X 3 M nL4X 3

u 3
m
b 4
M nX4 M nLX4 M nL2X 4 M nL3X4 M nL4X 4
e
r
M nX5 M nLX5 M nL2X 5 M nL3X 5
5
V.
N.
M nX6 M nLX6 M nL2X6 M nL3X 6
6

7
M nX7 M nLX7 M nL2X7
 Technetium Electron Number E.N.
11 12 13 14 15 16 17 18 19

TcL2 TcL3 TcL4 TcL5 TcL6

0
V
a
l TcL2X TcL3X TcL4X TcL5X
e 1
n
c 2
TcLX 2 TcL2X 2 TcL3X2 TcL4X 2 TcL5X 2
y

N TcLX 3 TcL2X 3 TcL3X 3 TcL4X3

u 3
m
b 4
TcX4 TcLX 4 TcL2X4 TcL3X 4 TcL4X 4
e
r
TcX5 TcLX 5 TcL2X 5 TcL3X5
5
V.
N.
TcX6 TcLX 6 TcL2X 6 TcL3X 6
6

7
TcX7 TcLX 7 TcL2X7
 Rhenium Electron Number E.N.
11 12 13 14 15 16 17 18 19

ReL 2 ReL 3 ReL 4 ReL 5 ReL 6

0
V
a
l ReL 2X ReL 3X ReL 4X ReL 5X
e 1
n
c 2
ReLX 2 ReL 2X 2 ReL 3X2 ReL 4X2 ReL 5X 2
y

N ReLX 3 ReL 2X 3 ReL 3X 3 ReL 4X3

u 3
m
b 4
ReX 4 ReLX 4 ReL 2X4 ReL 3X4 ReL 4X 4
e
r
ReX 5 ReLX 5 ReL 2X 5 ReL 3X5
5
V.
N.
ReX 6 ReLX 6 ReL 2X 6 ReL 3X 6
6

7
ReX 7 ReLX 7 ReL 2X7
 Iron Electron Number E.N.
10 11 12 13 14 15 16 17 18
V FeL FeL2 FeL3 FeL4 FeL5
a 0
l
e FeX FeLX FeL2X FeL3X FeL4X
n 1
c
y FeX 2 FeLX 2 FeL2X2 FeL3X2 FeL4X 2
2

N
FeX 3 FeLX 3 FeL2X3 FeL3X 3
u
3
m
b FeX 4 FeLX 4 FeL2X4 FeL3X 4
e 4
r
FeX 5 FeLX 5 FeL2X 5
V. 5
N'
FeX 6 FeLX 6 FeL2X6
6

7 FeX 7 FeLX 7
8 FeX 8 FeLX 8
 Ruthenium Electron Number E.N.
10 11 12 13 14 15 16 17 18
V RuL RuL2 RuL3 RuL4 RuL5
a 0
l
e RuX RuLX RuL2X RuL3X RuL4X
n 1
c
y RuX 2 RuLX 2 RuL2X2 RuL3X2 RuL4X2
2

N
RuX 3 RuLX 3 RuL2X 3 RuL3X 3
u
3
m
b RuX 4 RuLX 4 RuL2X4 RuL3X4
e 4
r
RuX 5 RuLX 5 RuL2X 5
V. 5
N'
RuX 6 RuLX 6 RuL2X6
6

7 RuX 7 RuLX7
8 RuX 8 RuLX 8
 Osmium Electron Number E.N.
10 11 12 13 14 15 16 17 18
V OsL OsL2 OsL3 OsL4 OsL5
a 0
l
e OsX OsLX OsL2X OsL3X OsL4X
n 1
c
y OsX2 OsLX2 OsL2X2 OsL3X2 OsL4X2
2

N
OsX3 OsLX3 OsL2X 3 OsL3X 3
u
3
m
b OsX4 OsLX4 OsL2X4 OsL3X4
e 4
r
OsX5 OsLX5 OsL2X 5
V. 5
N'
OsX6 OsLX6 OsL2X6
6

7 OsX7 OsLX7
8 OsX8 OsLX8
 Cobalt Electron Number E.N.
11 12 13 14 15 16 17 18 19
V CoL CoL2 CoL3 CoL4 CoL5
a 0
l
e
n CoX CoLX CoL2X CoL3X CoL4X
c 1
y
CoLX 2 CoL2X2 CoL3X2 CoL4X2
N 2 CoX 2
u
m
b CoX 3 CoLX 3 CoL2X 3 CoL3X 3
e 3
r
CoX 4 CoLX4 CoL2X 4 CoL3X4
V. 4
N.
CoX 5 CoLX5 CoL2X5
5

CoX 6 CoLX6 CoL2X6

6
 Rhodium Electron Number E.N.
11 12 13 14 15 16 17 18 19
V RhL RhL2 RhL3 RhL4 RhL5
a 0
l
e
n RhLX RhL2X RhL3X RhL4X
c 1
y
RhLX 2 RhL2X2 RhL3X2 RhL4X2
N 2 RhX 2
u
m
b RhX 3 RhLX 3 RhL2X 3 RhL3X 3
e 3
r
RhX 4 RhLX4 RhL2X 4 RhL3X4
V. 4
N.
RhX 5 RhLX5 RhL2X5
5

RhX 6 RhLX6 RhL2X6

6
 Iridium Electron Number E.N.
11 12 13 14 15 16 17 18 19
V IrL2 IrL3 IrL4 IrL5
IrL
a 0
l
e
n IrLX IrL2X IrL3X IrL4X
c 1
y
IrLX 2 IrL2X2 IrL3X 2 IrL4X 2
N 2 IrX 2
u
m
b IrX 3 IrLX 3 IrL2X 3 IrL3X 3
e 3
r
IrX 4 IrLX4 IrL2X 4 IrL3X 4
V. 4
N.
IrX 5 IrLX5 IrL2X 5
5

IrX 6 IrLX6 IrL2X 6

6
7 Ir(PR 3)H 7
 Nickel Electron Number E.N.
12 13 14 15 16 17 18 19 20
V NiL NiL2 NiL3 NiL4 NiL5
a
0
l
e
n NiX NiLX NiL2X NiL3X NiL4X
c 1
y
NiX 2 NiLX 2 NiL2X 2 NiL3X 2 NiL4X 2
N
u 2
m
b NiX 3 NiLX 3 NiL2X 3 NiL3X 3
e 3
r
NiX 4 NiLX 4 NiL2X 4 NiL3X 4
V.
N. 4
NiX 5 NiLX 5 NiL2X 5
5

NiX 6 NiLX 6 NiL2X 6

6
 Palladium Electron Number E.N.
12 13 14 15 16 17 18 19 20
V PdL PdL2 PdL3 PdL4 PdL5
a 0
l
e
n PdX PdLX PdL2X PdL3X PdL4X
c 1
y
PdLX 2 PdL2X 2 PdL3X2 PdL4X2
N 2 PdX2
u
m
b PdX3 PdLX 3 PdL2X 3 PdL3X 3
e 3
r
PdX4 PdLX4 PdL2X 4 PdL3X4
V. 4
N.
PdX5 PdLX 5 PdL2X5
5

PdX6 PdLX 6 PdL2X6

6
 MLX plots for Titanium, Manganese and Nickel

M anganese Electron Number E.N.

Titanium Electron Num ber E.N. 11 12 13 14 15 16 17 18 19 Nickel Electro n Nu mb er E.N.
V 8 9 10 11 12 13 14 15 16 17 18 MnL
5 12 13 14 15 16 17 18 19 20
MnL
2 MnL
3 MnL
4 MnL
6 V NiL NiL NiL NiL NiL
a TiL
2 TiL
3 TiL
4 TiL
5 TiL
6 TiL
7 V
0
a0
2 3 4 5
l0 a l
e l MnL
2X MnL3X MnL
4X MnL
5X e
n TiLXTiLX TiLX TiLX TiLX TiLX e1 n NiX NiLX NiL
2X NiL
3X NiL
4X
c 2 3 4 5 6 n c1
y
y1 c MnLX
2 MnL
2X2 MnL
3X2 MnL
4X2 MnL
5X2 NiX NiLX NiL
y2 N 2 2 2X2 NiL
3X2 NiL
4X2
N TiLX
2 TiL
2X2 TiL
3X2 TiL
4X2 TiL5X2 TiL
6X2 u2
MnLX MnL m
u2 N 3 2X3 MnL 3X3 MnL 4X3 b NiX NiLX NiL
m u3 3 3 2X3 NiL
3X3
e3
b TiX TiLX TiLX TiLX TiLX TiLX m r
e 3 3 23 33 43 53 b 4 MnX
4 MnLX
4 MnL
2X4 MnL 3X4 MnL 4X4 NiX
4 NiLX
4 NiL2X4 NiL
3X4
r3 e V.
N.4
r
V. TiX
4 TiLX
4 TiL
2X4 TiL
3X4 TiL
4X4 TiL
5X4 MnX
5 MnLX
5 MnL
2X5 MnL3X5 NiX NiLX NiL
N.4 5 5 2X5
V.5 5
N.
MnX
6 MnLX 6 MnL
2X6 MnL 3X6 NiX
6 NiLX
6 NiL
2X6
6 6

MnX
7 MnLX
7 MnL
2X7
7

Rule 1) Filled orbitals (18 electrons): Only possible for Ti when there are very small or compact
ligands since a further 14-electrons are required. E.g. [TiCp 2(CO)2]. TiCl4 is apparently an
8-electron compound but if the symmetry allowed contributions from the Cl p -orbitals are counted
then there are an extra 10 electrons which gives the value for EN = 18-electrons!
For M n, excellent for VN = 1 where also LBN = 6. but poor for VN = 3 and 5 since
LNB = 7 or 8 respectively AND higher VN for M n are rare since 3d orbitals are rapidly lowered
in energy by the increasing patrial +ve change on the M n centre.
For Ni, 18-electrons are found for NiL 4, NiL3X2 and (very rare) NiL 2X 4,. Higher VN's for Ni
not found since increase effective nuclear charge at this end of the d-block TM 's means the
I.P.'s too high. The special stability of square-planer, 16-electron NiL2X2 is associated with
the d8 configuration.

Rule 2) S teric saturation:For Ti: unusually high LBN's (and high co-ordination nos)
are commonly found, e.g. in 16-electron TiL 4X4, LBN = 8. For Ni. low LBN's (3,4,5) are found
since Ni already has 10 electrons and only requires 4 x L ligands to give 18e NiL 4 , e.g. Ni(CO) 4.

Rule 3) Electroneutrality rule:For Ti: since I.P.'s are low all 4 valency electrons are
accessible to most ligands, e.g TiI 4.
For M n, the increase of effective nuclear charge with increasing atomic number across the
d-block elements means that the higher VN's are only obtainable with the first row elements
as ligand atoms (since these for the strongest -bonds). Hence VN = 4 is found with F,
O, N, and C ligands, e.g. M nR 4, R = CH2SiM e3. VN = 7 is known only for [M n(=X)4]-, where
X = O or NR, the electron donation from the appropriate symmetry combination of the p=orbitals
of the X ligands and the negative charge resulting from the anion helps reduce the induced positive
charge on the M n centre. Nonetheless, the [M nO4]- and M n2O7 compounds are amongst the most
oxidising known (in aqueous acid). which shows these M n centres have exceptionally high partial
+ve charges.
 Back-donation--- but how much ?

back donation back donation

+
+ _  +
+
*
C H
Mo + + Mo +
C H
__ _ __
_
+

Chatt-Dewar H-H 0.84Å

(cf 0.74Å in H2)
 Partial charge on M
Positive Normal range Negative

+1 +0.5 0 -0.5 -1
MX ML
F NH 3

CO
MX2 F2 (NH 3)2 ML2
O

MX3 C 6H6 ML3

F3 (CO) 3 (NH 3)3

MX4 (PR 3)4 (NH ) ML4

F4 O2 H4 34

MX5 F5 (P(OR) 3)5 (NH 3)5 ML5

MX6 ML6
MF 6 MO3 MH6 M(CO) 6 M(C 6H6)(CO) M(P(OR)
3 3)6 M(C 6H6)2 M(PR 3)6 M(NH 3)6

Figure 7
Table 5. Exa mples of ligand functionality and den ticity.

Number of Number of Description Typical examples of

ligating orbitals a used ligand s
atoms in bond
formation
1 1 mono-dentane, mono-functional H, M e, NR2 (bent), NH3,
CO, H2
1 2 mono-dentate, bi-functional NR2 (planer), =CR2 , =O
1 3 mono-dentate, tri-functional N, CR (carbyne)
1 4 mono-dentate, tetra-functional quadruple bonds
2 1 and 1 bi-dentate, each mono-functional oxolate, acetate, ethylene-
diamine
2 2 and 1 bi-dentate, one b ifunctional the other mono- R2N(CH2)2NR
functional with planer CNR
2 1(MO) bidentate, mono functional -etheneb
2 1 + 1(AO's) bi-dentate, bifunctional C2H4 in
metallacyclopropaneb
3 2(MO's) tridentate, bi-functional -allyl
5 3(MO's) penta-dentate, trifunctional -cyclopentadienyl
6 3 (MO's) hexa-dentate, tri-functional -benzene
a Essentially atomic orbitals (AO) unless otherwise indicated. MO indicates a molecular orbital.
b These are alternative descriptions. for the bonding of e thene.
 Table 6 Rules for classification of cov alent molecules and molecular ions

Rule for L.B.N.

Initial class reduction V.N. given by given Limits
to E.N.C. by

MXx neutral - x x x Š Me

[MXx]m- anions X- L x-m x mŠx

[MXx]m+ cations X+  Z x-m x mŠx

MLl neutral - x=0 l availability of M

orbitals, 18e rule

[ML l]m- anions L- ’ LX m l+m availability of

ligand orbitals

[ML l]m+ cations L+ ’ X m l m Šn

MLlXx neutral - x l+x x Š Me,

availability of
M orbitals

[MllXx]m- anions X- ’ L, x-m (m Š x) l+x

As for [ML]m-
then and [MX]m-
L- ’ LX m - x (l+x > m> l + m + anions
x) x
[ML lXx]m+cations L+ ’ X, x + m ( m < l) l+x As for [ML]m+
then and [MX]m+
X +’ Z 2l + x - m l+x cations
(m>l)
Table 9. Determination of MLXZ class and reduction to the neutral class of oxyg en
derivatives; where O is a X 2 class ligand.

Molecule or Ion
Class Rule Equivalent Neutral Class
C O2 M( X 2) -- MX 4

C O32- M X 2( X 2-)2 X 2-X MX 4

MoO2Cl2 M( X 2)2X2 -- MX6b

SO3 M( X 2)3 -- MX6

SO2Cl2 M( X 2)2X2 -- MX 6

Me2C O [M( X 2)2X2] -- MX 4

MoO42- [M( X 2)2( X -) X 2- X MX 6b

ReO4- [M( X 2)3( X -) X 2- ’ X MX 7b

NO2- [M( X 2)( X 2-)] X 2-’ X MX 3

PHO32- [M( X 2)( X 2-)2X] X 2- ’ X MX5

[VO(H2O)4]2+ [M( X 2)L2(L+)2 L+’ X ML2X4b

VO(acac)2 [M X 2(LX)2] -- ML2X4b

[VO(SCN)4]2- a [M( X 2)-X3X- ] X 2-’ LX ML2X4b

X- ’ L

a The V = O distance = 1.62Å so O is classified as ( X )-.b The metal centre has empty d-
2
orbitals, if p-lone pair electrons on the oxygen donate to the metal the number of L-
functions increases by one or more according to symmetry considerations.
 Table 3. Summary of new definitions for the classification
of covalent compounds

Term Short Symbol

A one-electron ligand function X
Number of X ligands x
A two-electron ligand function L
Number of L ligands l
Electron number of ligand of class LlXx L.N. = 2l + x
A mono-functional Xx -ligand-atom Xx = 1
A poly-functional Xx -ligand atom Xx >1
General representation for the class of a MLlXx
covalent compound
Electron Number of Mo in MoLlXx E.N. = 6 (for Mo) + 2l + x
Valency Number V.N. = x
Ligand Bond Number L.B.N. = l + x
n of dn n = 6(for Mo) - x -(2z)
Number of electrons in the valency shell of the Me
metal
Equivalent Neutral Class E.N.C.
 Table 4. Classification of reactions by the reaction products

Change in Ll and/or Xx Change in Name of reaction

E.N. V.N.
-Ll then +L'l 0 0 Ll -substitution
-Xx then +X'x 0 0 Xx -substitution
+Ll +2l 0 Ll-addition
-Ll -2l 0 Ll-elimination
+Xx +x +x Xx-oxidative-addition
-Xx -x -x Xx-reductive-elimination
+L then -Xa +1 -1 reductive-replacementa
-L then +Xb -1 -1 oxidative-replacementb
-Ln then +X2n (n=1) 0 +2 replacement-additionc
+Ln then -X2n (n=1) 0 -2 replacement-eliminationd
 12 13 14 15 16 17 18

0
ELECTRON NUMBER E.N.
V
A
L -
E -L +L( +X )
+ X+
1 N ML X ML X -
C l-1 x l x ML X ]
l x+1
Y

N +X
U
2 M +X2
B +X2 +X+
E
R

V. +
ML X ]
3 N. l x+1
+ X-
MLl Xx+2
[MLl -1Xx-1] + MLl -1X x+2
PRODUCT
.

MX6 MLX ML2X 6 ML3X 6

6
6
EV
I
9.5
O
N 9.0
I
S 8.5
A
T 8.0
I
7.5
O
N 7.0

E 6.5
N
E
6.0
R
5.5
G
Y 5.0
O 1 2 3 4 5 6 V.N
.
indicates ionisation of thendelectrons
indicates ionisation from Mo=Mo bonds (since these compoundsoare
. d

Valency Number