Ifas Inorganic Tec

Index
Chapter 1 Introduction to Coordination Chemistry

1.1. Introduction 1
1.2. Double Salt and Coordination Compounds 2
1.3. Some important terminologies of coordination compounds 3
1.4. Classification of ligands 5
1.5. Nomenclature of the coordination complexes 7
Chapter 2 Isomerism of the coordination compounds

2.1. Introduction 9
2.2 Structural isomerization 9
2.3. Steroisomerism 13
Chapter 3 Theories of coordination chemistry

3.1 Early theories to explain bonding in coordination compounds 33
3.2. Later theories to explain bonding in coordination compounds 35
Chapter 4 Term symbol and electronic spectra of the coordination compounds

4.1. Term Symbols 76
4.2. Electronic Spectra of the Coordination Complexes 92
4.3 Charge Transfer Spectra 125
129
Chapter 5 Magnetism of the coordination complexes
5.1. Introduction 130
5.2. Origins of Magnetic Behavior 130
5.3. Types of Magnetism 131
5.4. Temperature Dependence of Magnetic Susceptibilities 132
5.5. Deviations from Spin-Only Behavior 133
Chapter 6 Stability and the reaction mechanism of the coordination complexes

6.1. Stability of the coordination compounds 141
6.2. Inorganic Reaction Mechanism 151
6.3. Summary 183
6.4 HOTS-High order thinking skills 187
212
Chapter – 7 Introduction to organometallic compounds and their stability
7.1. Introduction of Organometallic Compounds 213
7.2. Classification of Organometallic Compounds 213
7.3 Electron Rule 215
222 Inorganic Chemistry
Chapter 8 Interaction of metal with carbonyl & nitrosyl ligand

8.1. Metal Carbonyl Clusters 221
8.2. Zintl Ions 229
8.3. Isolobal Species 230
8.4. Metal carbonyls 243
8.5. Phosphine Ligand 259
8.6. Metal Nitrosyls 260
8.7. Fluxional Behaviour of the Organometallic Compounds 263
8.8. HOTS- High Order Thinking Skills 267
Chapter 9 Reactions of the organometallic compounds & metal carbenes

9.1. Reaction in Organometallic Chemistry 275
9.2. Metal Carbenes 284
9.3. Metal Alkyl, Alkene and Allyl Complexes 287
9.4. Organometallic Compounds of Main Group Elements 296
Chapter 10 New Generation Of Organometallic Chemistry : Metallocene Compounds

10.1. Introduction to Metallocenes 299
10.2. Cyclopentadienyl (Cp) Complexes 299
10.3. Bent Sandwich Compounds 304
10.4. Half Sandwich Compounds 305
10.5. Cycloheptatriene Complexes 306
10.6. Cyclooctatetraene Complexes 308
Chapter 11 Applications of organometallic compounds: homogeneous catalysis

11.1. Homogeneous Catalysis 312
11.2. Hydrogenation of Alkenes by Wilkinson’s Catalyst 314
11.3. Hydroformylation or Oxo Process 317
11.4. Wacker Process of Alkenes 320
11.5. Monsanto Acetic Acid Process 322
11.6. Alkene Polymerization: Ziegler-Natta Catalyst 323
11.7. Water Gas Reaction: Fischer-Tropsch Process 324
11.8 Catalytic Deuteration 325
11.9 Olfien Metathesis 326
11.10 Summary 334
11.11. HOTS- High Order Thinking Skills 336
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Interaction of metals with carbonyl and nitrosyl ligands 223
Chapter 8
Interaction of Metal with Carbonyl &
Nitrosyl Ligand
8.1. Metal Carbonyl Clusters
The compound in which several metal atoms are bound together directly through M-M bonds are called as cluster.
Metal carbonyl clusters are classified into two categories:
1. Low nuclearity carbonyl clusters
2. High nuclearity carbonyl clusters
8.1.1. Low Nuclearity Carbonyl Clusters (LNCC):

The first metal carbonyl cluster having M-M bond is Mn2(CO)10. The low nuclearity carbonyl clusters contain metal atoms <4.
Calculation of number of M-M bonds using 18/16-electron rule in LNCC:

The procedure for calculation of number of M-M bonds in a compound involves the following steps:
Step I:
Calculate total valence electrons (TVE) on central metal in the compound (say it is x) which is equal to the number of valence
electrons of the metal plus the number of electrons from each ligand and the charge.
Substract A from n x 18 (where n is the number metal atoms in the compound), say it is M-M bonds
𝟏𝟖 × 𝐧 −𝒙
M – M bonds =
𝟐
n = number of metal atoms
x = total no of valence e- (metal + legand e-s)
Example:
a. Mn2 (Co)10 – valence electron count
2 Mn 14 electron
10 CO 20 electron
Total = 34 electron
18 × n −𝑥
M – M bonds =
2
18 × 2 −(14+20)
=
2
36−34 2
M –M bonds = = =1
2 2
Therefore, in Mn2 (Co)10 only one M-M bonds is present.

In Mn2 (Co)10 number of bridged CO ligand is Zero.

b. Co2(CO)8 - valence electron count

2 Co 18 electron
8 CO 16 electron
Total = 34 electron
18 × 2 −(18+16)
M–M =
2
36−34
= =1
2
i.e. Co2(CO)8 only one M-M bond is present.
In solution state no bridging CO,Only one IR frequency but in solid state it has two CO bridging.
- Solid Co2 (Co)8 dissolve in n –hexane, structure changes are observed in which bridged CO ligands changes to terminal CO
ligands.
c. Fe2(Co)9 - valence electron count

2 Fe 16 electron
9 CO 18 electron
Total = 34 electron
18 × 2 −(16 +18)
M – M bonds =
2
36−34
= =1
2
In Fe2(CO)9 , one M-M bond is present.
In Fe2(CO)9 , 3 – CO are bridged and 6 terminal CO ligands.
d. M3(CO)12 M= Fe, Ru, Os

18 × 3−(24 + 24)
M–M =
2
54 −48
=
2
M-M bonds =3
Ru3(CO)12 , Os3(CO)12 bridged CO ligands zero
In Fe3(CO)12 ,2- bridged CO ligands are present

Out of 3 metals, 2 metals Co-ordination number = 7 And one Co-ordination number = 6
e. Co4(CO)12, Ir4(CO)12
18 × 4 −(36 + 24)
M–M =
2
72 − 60
= =6
2
Solid Co4(CO)12 :- Bridged CO = 3 Solid Rh4(CO)12 :- Bridged CO = 3
Solution Co4(CO)12 :- Bridged CO = 9
f. Ir4(CO)12 :
In Ir4(CO)12 number of bridged CO ligand = zero
g. Os4(Co)14 :-
Number of M – M bonds are = 6
h. Os4(Co)15 :
In Os4(Co)15 M – M bonds = 5
i. Os4(Co)16 :-
In Os4(Co)16 M – M bonds = 4
Except Os4(Co)14, in remaining all Os – CO clusters bridging CO ligand are zero
Os4(CO)16 is analogous to cyclobutane conformation.

To Determine the Unknown Quantity Using 18-Electron Rule:

a. [(ƞ5- C5H5)W(CO)x]2 (W- W single bond)
2 X 5 + 2 X 6 + 2 + 4x = 36
24 + 4x = 36 ; i.e. x=3
b. [(ƞ5- C5H5)Mn(CO)x]2 (Mn = Mn double bond)

2 X 5 + 2 X 7 + 4 + 4x = 36
28 + 4x = 36 ; i.e. x=2
To Determine the Expected Charge on the Complex Ions Using 18-Electron Rule
a. [Co(CO)3]x
9+3 X 2 + x = 18
15 + x = 18
x = 18 – l5 = 3
Therefore, charge on the complex ion is = -3
b. [(OC)3 Ni-Co(CO)3]x
3 X 2 + 10 + 2 + 9 + 3 X 2 + x = 36
33 + x = 36
x = 36-33 = 3
Therefore, charge on the complex ion = -3
c. [(ƞ5 – C5H5)3Ni3(µ3 - CO)2]x (Three Ni-Ni bonds)

15 + 30 + 2 X 2 + 3 X 2 + x = 54
15 + 30 + 4 + 6 + x = 54
55 + x = 54 ; i.e. x = 54 - 55= -1
Therefore, charge on the complex ion = + 1

To Identify the Transition Metal in a Complex Using 18-Electron Rule:

a. [(µ5-C5H5)M(CO)3]2 (M is first row transition metal and one M- M single bond)
Let x be the number of electrons contributed by the metal
10 + 2 + 2x + 12 = 36
2x = 36 – 24 = 12
x=6
Therefore, metal is Cr (3d55s1)
b. [M(µ6-C6H6) (CO)2]2 (M is the second row transition metal and two M= M bond)
2x + 4 + 2 x 6 + 4 * 2 = 36
2x = 36- 24 ; i.e. 2x = 12 or x = 6
Therefore, metal is Mo(4d55s1).
c. [M (µ3 -C5H5) (CO) 5] (M is 3d-series transition metal)

x + 3 + 5 X 2 = 18
x = 18-13
=5
Therefore, metal is V (3d3 4s2)
8.1.2. High Nuclearity Carbonyl Clusters:

If metals atoms is more than 5 then called as HNCC.
𝟏𝟖 × 𝐧 −𝐱
formula is not applicable, if cluster with more than 4 metal atoms.
𝟐
The structures of the HNCC can be, determined by skeletal or framework electron counts with the help of Wade's rule.
a. Calculate total electron count (TEC).
b. Add to TEC the valence electrons for interstitial atom, for example, 1 for H, 4 for C, 5 for N, 5 for P and so on.
c. Calculate the skeletal electron pairs(S)
Based on wade’s rules:

𝐓𝐄𝐂−𝟏𝟐 × 𝐧
S=
𝟐
S = Skeletal e- pair
n = number of metals atom
The structure according to Wades rule,
If Skeletal electron pair
n -1, super closo
n hyper closo
n +1 closo
n+2 nido
n+3 Arachno
n+4 hypo
n+5 klado
The Number of vertices = S – 1

C│H│N│P│As│S→ Encapsulated atoms

Table 8.1: The valence electron counts corresponding to the various structural classifications for main group and transition
metal clusters are summarized.
Structure Boranes Transition Metal Clusters

Type TEC Skeletal Electron Pairs TEC Skeletal e- pair
Closo 4n + 2 n+1 14n + 2 n+1
Nido 4n + 4 n+2 14n + 4 n+2
Arachno 4n + 6 n+3 14n + 6 n+3
Hypho 4n + 8 n+4 14n + 8 n+4
Klado 4n+10 N+5 14n+10 N+5
High nuclear metal carbonyl clusters
−
- HCo6(Co)15 → H – atom Encapsulated
- Rh6P(Co)3−
22 → P atom Encapsulated
−
- Fe4N(Co)12 → N atom Encapsulated
- Rh6As(Co)3−
22 → As atom Encapsulated
a. Rh6(Co)16 :- Total valence electron count(TEC)

6 Rh 54 electron
16 CO 32 electron
Total = 86 electron
TEC−12 ×N
S =
2
86− 12 ×6 86 − 72
S = = =7
2 2
6 + 1 = 7 → i.e. (n+1) Closo
Number of vertices =S–1
=7–1=6
6 vertices are occupied by 6 metals
So, ClosoOctahedran

b. Os5C(Co)15 :
TEC = 40 + 4 + 30
= 74
74 − 12 × 5
S =
2
74− 60
= =7
2
i.e n + 2 = 7
5 + 2 = 7 Nido
=7–1=6
So, Nido
c. Os5(Co)16 :
TEC = 40 + 32 = 72
72 − 12 × 5
S =
2
72 − 62
S = =6
2
i.e. n + 1 = 6 →Closo
Number of vertices = S – 1
= 6 – 1 = 5 (TBP)
So, Closo TBP
d. Fe4C(𝐂𝐨)𝟐−
𝟏𝟐 :
TEC = 32 + 4 + 24 + 2= 62
62 − 12 × 4
S =
2
62 − 48
S = =7
2
i.e n + 3 = 7 (Arachno)
= 7 – 1 = 6 (oh)
So, ArachnoOctahedran
e. H3Ru4(𝐂𝐨)−
𝟏𝟐 :
TEC = 3 + 32 + 24 + 1 = 60
60 − 12 × 4
S =
2
60 − 48
S = =6
2
i.e. n + 2 = 6 →Nido
= 6 – 1 = 5 (TBP)
So, Nido TBP

f. Ru5N(𝐂𝐨)−
𝟏𝟒 :-
TEC = 40 + 5 + 28 + 1 = 74
74 − 12 × 5
S =
2
74 − 60
S = =7
2
i.e. n + 2 = 7 →Nido
Number of vertices= S – 1
= 7 – 1= 6 (oh)
So, Nido oh
g. Fe4N(𝐂𝐨)−
𝟏𝟐 :-
TEC = 32 + 5 + 24 + 1 = 62
62 − 12 × 4
S =
2
62 − 48
S = =7
2
i.e. n+ 3 = 7 →Arachno
= 7 – 1 = 6 (oh)
So, Arachno oh
h. Os7(Co)21:
TEC = 56 + 42 = 98
98 − 84
S =
2
=7
i. Os8(𝐂𝐨)𝟐−
𝟐𝟐 :
TEC = 64 + 44 + 2 = 110
110 − 96
S = =7
2
j. Os10C(𝐂𝐨)𝟐−
𝟐𝟒 :
TEC = 80 + 4 + 48 + 2 = 134
134 − 120
S = =7
2
• In above 3Os clusters number of metal atoms are increasing but no change in skeletal e- pair.
• In Os7(Co)21 one of the triangular faces of polyhedran capped by Os metal
• In Os8(Co)2−
22 , two triangular faces of polyhedran capped by 2 Os metals.
• In Os10C(Co)2−
24 , four triangular faces of polyhedran capped by 4 Os metals.
• Capping atoms only increasing TEC but does not change skeletal e- pair

8.2. Zintl Ions
The ionic clusters of main group elements are called Zintl ions. Since these ions have no ligand, these are also known as nacked
clusters Zintl ions are also classified into closo, nido, arachno and hypho clusters
It is also based on the Wades rules if total electron count is equal to:
= 4n + 2 Closo
= 4n + 4 Nido
= 4n + 6 Arachno
= 4n + 8 Hypho
= 4n + 10 Klado
Where; n= number of metal atoms in the Zintl ion.
Examples:
1. P4:
Valence electron count for P4 is as follows:
P is group 5 element so it has 5 valence electrons = 5 × 4
Total valence electron count = 20 electron
i.e. 4 = 4 × 4 = 16 + 4 = 20
So, structure is 4n + 4 → Nido cluster
2. 𝐒𝐧𝟒−
𝟗 :
Sn is group 4 element so it has 4 valence electrons = 4 × 9
Charge = 4
i.e. 4n = 4 × 9 = 36 + 4 = 40
So structure is 4n + 4 = Nido cluster.
3. 𝐒𝐧𝟐−
𝟗 :
Sn is group 4 element so it has 4 valence electrons = 4 × 9
Charge = 2
i.e. 4n = 4 × 9 = 36 + 2 = 38
So, structure is 4n + 2 = Closo
Ge4−
9 → Nido
Ge2−
9 → Closo
4. 𝐁𝐢+𝟑
𝟓 :
Bi is group 5 element so it has 5 valence electrons = 5 × 5
Charge = - 3
i.e. 4n = 4 × 5 = 20 + 2 = 22
So, structure is 4n + 2 = Closo

5. 𝐁𝐢𝟐−
𝟒 :
Bi is group 5 element so it has 5 valence electrons = 5 × 4
Charge = 2
Total valence electron count = 20 +2=22
i.e. 4n = 4 × 4=16 = 16 + 6= 20
So, structure is 4n + 4 = Arachno
Tetrahedral Trigonal Capped Trigonal

Bipyramidal Prismatic
[Ge4]4- [Sn5]2- [Ge9]2-
[Sn4]4- [Pb5]2- [Ge9]3-
[Pb4]4- [Sn9]3-
Monocapped Bicapped
Square-antiprismatic Square-antiprismatic
[Ge9]4- [Ge10]2-
[Sn9]4-
[Pb9]4-
Fig. 8.1: Schematic representations of structure types for selected Zintl ions
8.3. Isolobal Species
These are proposed by hofmann
Rules:
1. Molecules with similar chemical properties
2. Molecule with similar FMO’s
3. Molecules with similar symmetry properties
4. Molecules with similar energies
5. Molecules with similar number of e-s

EX:
Mn(Co)5 17e- (Lack of 1 ligand forOd and 1 e for stability)
CH3 7e- (Lack of 1 ligand for Td and 1 e foe octet)
Cl 7e-
Cl + e-→ Cl- 8e-
Mn(Co)5 + e-→ [ Mn (Co)5]-
Table 8.2: Some Isolobal Fragments of Transition Metals and Main Group Elements
CH4 CH3 CH2 CH C
Cr(CO)6 Mn (CO)5 Fe (CO)4 Mn(CO)4 Fe(CO)3
[Mn(CO)6]+ [Fe(CO)5]+ [Cr (CO)5]- Cr (CO)5 Ni (CO)3 Co(CO)3 Ni(CO)2
Fe(CO)5 Co (CO)4 CpCo(CO) CpCr(CO)2 Cr(CO)4
Ni (CO)4 CpFe(CO)2 [Co (CO)4]- CpNi CpCo
CpMn(CO)3 V(CO)6 CH+3 CH+2 CH+
CH-3 CH-2 CH-S P
Isolobal analogy of transition metal cluster and Boranes:

Os8(CO)23 or [Os8(CO)24]2+ :
TEC = 8 x 8 + 23 x 2 = 64 + 46 = 110
PEC = 110 - 8 x 12 = 110- 96 = 14
PEC/2 = 14/2 = 7 = 8 - 1 (n - 1)
Super hyper closo(bi-capped closo)
[B8H8 ]2+:
Number of skeletal electron pairs = (8 * 2 - 2)/2
= 14/2 = 7
= 8 – 1 (n - 1)
Super Hyper Closo
Os8(CO)23↔[Os8(CO)24]2+↔ [B8H8]2+
𝒐 𝒐
Similarly, hyper closo boranes BnHnareisolobal with hyper closo(i.e., polyhedron with one face metal capped), closo boranes are
isolobal with closo(i.e., regular polyhedron like TBP, Oh), nido boranes are isolobal with nido(i.e., polyhedron with one vertex
unoccupied), arachno boranes are isolobal with arachno(i.e., polyhedron with two vertices unoccupied) and hypho boranes are
isolobal with hypho(i.e., polyhedron with three vertices unoccupied) metal clusters.
A transition metal clusterand a borane are isolobal if both have same number of vertices. Some examples are given below:
1. Os6(CO)18 :
TEC = 6 x 8 + 18 x 2 = 48 + 36 = 84
PEC = 84 – 6 x 12 = 84 – 72 = 12
PEC/2 = 12/2 = 6 (= n)
hyper closo
B6H6:
Number of skeletal electron pairs = (6 * 2) / 2 = 6 (= n)
(hyper closo)
Os6(CO)18↔ B6H6
𝑜

2. [Os6(CO)18]2- :
TEC = 6x 8 + 18 x 2 + 2 = 48 + 36 + 2 = 86
PEC = 86- 6 x 12 = 86 - 72 = 14
PEC/2 = 14/2 = 7 = 6 + 1 (n + 1)
closo (regular octahedron)
[B6H6 ]2- (regular octahedron)
Number of skeletal electron pairs = (6 x 2+ 2)/2 = 14/2
= 7 (n + 1)
closo
[Os6(CO)18]2-↔ [B6H6]2-
𝒐
3. [Os5(C0)15]2- :
TEC = 5 x 8 + 15 x 2 + 2 = 40 + 30 + 2 = 72
PEC = 72 - 5 x 12 = 12
PEC/2 = 12/2 = 6 (n + 1)
closo
[B5H5 ]2-
Number of skeletal electron pairs = (5 x 2 + 2)/2
= 6 (n + 1)
(closo)
[Os5(CO)15]2-↔ [B5H5]2-
𝒐
4. Fe4C(CO)13:
TEC = 4 x 8 + 4 + 13 x 2 = 32 + 4 + 26 = 62
PEC = 62 – 4 x 12 = 62 – 48 = 14
𝑃𝐸𝐶 14
= = 7 (n+4) Archno
2 2
[B4H4 ]6-:
4 𝑥 2+6 14
Number of skeletal electron pairs = =
2 2
= 7 (n + 4) arachno
Fe4C(CO)13↔ [B4H4]6-
𝒐
5. Fe5C(CO)15:
TEC = 5 x 8 + 4 + 15 x 2 = 40 + 4 + 30 = 74
PEC = 74 – 5 x 12 = 14
𝑃𝐸𝐶 14
= = 7(n + 2) nido
2 2
[Fe5(CO)15]4-:
TEC = 5 x 8 + 15 x 2 + 4 = 40 + 30 + 4 = 74
PEC = 74 – 5 x 12 = 14
𝑃𝐸𝐶 14
= = 7(n + 2) nido
2 2
[B5H5]4-:
5 𝑥 2+4 14
2 2
= 7 (n + 2) nido
Fe5C(CO)15↔ [Fe5(CO)15]4-↔ [B5H5]4-
𝒐 𝒐

6. [HCo6(CO)15]-:
TEC = 1 + 6 x 9 + 15 x 2 + 1 = 1 + 54 + 30 + 1 = 86
PEC = 86 – 6 x 12 = 14
𝑃𝐸𝐶 14
= = 7 (n+1) closo
2 2
[Co6(CO)15]2-:
TEC = 6 x 9 + 15 x 2 + 2 = 54 + 30 + 2 = 86
PEC = 86 – 6 x 12 = 14
𝑃𝐸𝐶 14
= = 7 (n+1) closo
2 2
[Fe6(CO)18]2-:
TEC = 6 x 8 + 18 x 2 + 2 = 48 + 36 + 2 = 86
PEC = 86 – 6 x 12 = 14
𝑃𝐸𝐶 14
= =7 (n+1) closo
2 2
[B6H6 ]2-:
6 𝑥 2+2 14
2 2
= 7 (n+1) closo
7. [CpNi]6 :
TEC = 6 x 5 + 6 x 10 = 30 + 60 = 90
PEC = 90 – 6 x 12 = 90 – 72 = 18
𝑃𝐸𝐶 18
= = 9(n + 3) Arachno
2 2
[B6H6]6-:
6 𝑥 2+6 18
Number of electron pairs = =
2 2
= 9(n + 3) arachno
[CpNi]6↔ [B6H6]6-
𝒐
Skeletol e- pairs (or) Frame work e- pair for higher boranes:

Table : 8.3
Frame work e-pair/skeleton e-pair Framework e-s /skeleton e-s
Closo (n+1) 2 (n+1)
Nido (n+2) 2 (n+2)
Arachno (n+3) 2 (n+3)
Hypo (n+4) 2 (n+4)
Klado (n+5) 2 (n+5)
→ B2H6 – Nido – n + 2 = 2 + 2 = 4 pairs = 8e-
→ B4H10 – Arachno – n + 3 = 4 + 3 = 7 pairs = 14e-
→ B5H9 – Nido – n + 2 = 5 + 2 = 7 pairs = 14e-
→ B5H11– Arachno – n + 3 = 5 + 3 = 8 pairs = 16e-s
→ B6H10 – Nido – n + 2 = 6 + 2 = 8 pairs = 16e-
→ B10H14 – Nido – n + 2 = 10 + 2 = 12 pairs = 24e-

→ B5H56− – Arachno – n + 3 = 5 + 3 = 8 pairs = 16e-

Classify the heteroboranes compounds into Closo, Nido, Arachno, and Hypo
1. NCB10H11
N=BH2
C=BH
(BH2) (BH) B10H11
B12H14Closo
Bn Hn + 2 →Closo
Bn Hn + 4 →Nido
Bn Hn + 6 →Arachno
Bn Hn + 8 →Hypo
Bn Hn + 10 →Klado
2. PCB9H12 :-
(BH2) (BH) B9H12
B11H15 Nido
3. GeC2B9H11 :-
(BH) (BH)2 B9H11
B12H14Closo
4. SB9H11 :-
(BH3) B9H11
B10H14Nido
5. SB9H13 :-
(BH3) B9H13
B10H16Arachno
6. CB10H14 :-
(BH) B10H14
B11H15Nido
7. SiC2B2H10 :-
(BH) (BH)2 B4 H10
B7H13Arachno
8. B4H6(CoCp)2 :-
B4H6(BH)2
B6H8Closo
9. C2B7H11CoCp :-
(BH)2 B7H11 (BH)
B10H14 Nido
10. C2B9H11Ru(Co)3 :-
(BH)2 B9H11 (BH)
B12H14Closo
11. C2B4M6[Ni (pph3)2] :-
(BH)2 B9H6 (BH)
B7H9 Closo
12. B5H10(FeCp) :
B5H10B
B6H10Nido

• Calculation of different types of bonding in higher boranes:

• Total no. of bonds = ½ (3B + H)
• Total no. of 2C – 2e-bonds = ½ (B + H)
• Total no. of 3C – 2e-bonds = B
B–H Total bonds

12
B2H6 – 4 B2H6 = ½ (3(2) + 6) = =6
2
22
B4H10 – 6 B4H10 = ½ (3(4) + 10) = = 11
2
24
B5H9 – 5 B5H9 = ½ (3(5) + 9) = = 12
2
26
B5H11 - 8 B5H11 = ½ (3(5) + 11) = = 13
2
28
B6H10 - 6 B6H10 = ½ (3(6) + 10) = = 14
2
44
B10H14 - 10 B10H14 = ½ (3(10) + 14) = = 22
2
Total no. of 2C – 2e- bonds

8
B2H6 = ½ (2 + 6) = = 4
2
14
B4H10 = ½ (4 + 10) = =7
2
14
B5H9 = ½ (5 + 9) = =7
2
16
B5H11 = ½ (5 + 11) = =8
2
16
B6H10 = ½ (6 + 10) = =8
2
24
B10H14 = ½ (10 + 14) = = 12
2
Total no. of 3C – 2e- bonds

B2H6 = 2
B4H10 = 4
B5H9 = 5
B5H11 = 5
B6H10 = 6
B10H14 = 10
STYX Number [a b c d]:-
c= B – B → 2C- 2e- bonds
group

B2H6 = [2 0 0 2]
B4H10 = [4 0 1 2]
B5H9 = [4 1 2 0]
B5H11 = [3 2 0 3]
B6H10 = [4 2 2 0]
B10H14 = [4 6 2 0]
SYTX number codified in the form of 4-digit number

STYX number indicating the structure of boranes
A. Structure Prediction forHeteroboranes And Organometallic Clusters

• The 18-electron rule was adequate for predicting stabilities of small organometallic clusters.
• We have seen that Wade's rules allow us to make predictions about borane structures based on the number of
framework electrons.
• These rules also are adequate for most carboranes, metallacarboranes, and other heteroboranes.
• Furthermore, organometallic clusters that are not derived from boranes can be dealt with in a similar fashion. More
sophisticated extensions are required for complex larger clusters.
• We viewed the [C2B9H11]2- anion as a ligand analogous to [C5H5]- Perhaps a more useful approach is to view [Fe(η-C5H5)]-
as a replacement for a BH fragment, i.e., a species, like BH, provides three orbitals and two electrons.
• In other words, we might predict that we can replace the BH unit with any species that is isolobal with it.
Table 8.4 Electrons available for framework bonding for various organometallic fragmentsFramework electrons
Fragment Cr, Mo, W Mn, Tc, Re Fe, Ru, Os Co, Rh, Ir Ni, Pd, pt
M (η5 -C5H5) -1 0 1 2 3
M (CO)2 -2 -1 0 1 2
M (CO)3 0 1 2 3 4
M (CO)4 2 3 4 5 6
• Possibilities include (in addition to [Fe (η5 -C5H5)]-Fe(CO)3, Co(η5-C5H5), Ni(CO)2, Al-R, or Sn (the transition metal
fragments are 14-electron species.
• Our electrons short of 18, and the non-transition metal units are four electrons short of an octet). Similarly, one could
imagine a CH unit of a carborane being replaced by a species which can provide three orbitals and three electrons.
• Fitting this description are Co(CO)3, Ni(η5-C5H5), and P.
• The table consist of organometallic fragments and the number of electrons each can provide to a framework structure.
• You can construct your own table by remembering that each transition metal has twelve electrons associated with it
that are reserved for non-framework bonding.
• Electrons in excess of twelve can be contributed to the framework (thus the 14-electron species above contribute two
electrons each, and the 15-electron species contribute three electrons, etc.).
• If there are fewer than twelve electrons in the fragment, the framework. must make up the difference [e.g., Mn (CO)2,
and an 11-electron species, is assigned a framework contribution of -1].
• One of our goals here is to be able to predict the structure of a cage or cluster from its molecular formula.
• We do this by first finding the number of framework electrons.
• The structure will then be predicted to be closo, nido, or arachno if the number of framework electrons is 2n + 2, 2n +
4, or 2n + 6 respectively,
As an example let us consider B3H7[Fe(CO)3]2, for which n equals five

B3H7[Fe(CO)3]2
The three BH units and the two Fe(CO)3 units contribute two electrons each and the four extra hydrogen atoms contribute one
electron each to give a total of 14 framework electrons:
2Fe(CO)3: 2 x 2 = 4e-
3BH: 3 x 2 = 6e-
4H: 4 x 1 = 4e-
Total = 14e-
Since n = 5, we see that there are 2n + 4 framework electrons and we predict a nido structure which is found experimentally.
The square pyramidal structure can be thought of as resulting from substitution of two BH units with two Fe(CO)3 units in B5H9.
Let us apply these procedures to the nonborane molecule, Rh6(CO)16, for which n equals six. Each of the six Rh(CO) 2 units
contribute one electron to the framework; while the four extra CO molecules provide eight electrons:
6Rh(CO)2: 6 x 1 = 6e-
4CO: 4 x 2 = 8e-
Total = 14 e-
Thus we have 14 framework electrons with the complex fitting the 2n + 2 categories and predicted to have a closo structure.
There are two terminal CO groups per Rhodium and four bridging carbonyl groups which are placed on alternate triangular faces.
Another method for obtaining the number of framework electrons starts by counting the valence electrons of all of the metal
atoms and then adds of the electrons donated by the ligands:
6Rh: 6 x 9 = 54e-
16CO: 16 x 2 = 32e-
Total = 86e-
Twelve of these electrons per Rhodium (a total of 72) will be used for nonframework bonding leaving 14 for framework bonding.
Thus there are seven bonding pairs in the framework corresponding to 2n + 2 electrons and, as above a closo structure is
predicted.It is worth noting that the 18-electron rule fails for Rh6(CO)16, while Wade's rules are entirely successful.There are
exceptions to Wade's rules, even among modest-sized clusters. In some cases large transition metals cause geometrical
distortion.

Fig. 8.2: Structures of B3H7[Fe(CO)3]2 and Organometallic Derivatives of B5H9
Within this table we see three strcutures (tetrahedron, butterfly, and square plane) for tetranuclear metal clusters. The
tetrahedron is a 60-electron cluster, while the butterfly and square plane clusters have 62 and 64 electrons, respectively. When
we go from a tetrahedron to a butterfly, one of the edges of the tetrahedron is lengthened corresponding to bond breaking.
Table 8.5: Relationship between geometry, molecular orbitals, and cluster valence electrons
Geometry No. Of metal atoms Bonding molecular orbitals Cluster electrons Examples
Monomer 1 9 18 Ni(CO)4
Dimer 2 17 34 Fe2(CO)9
Trimer 3 24 48 Os3(CO)12
Tetrahedron 4 30 60 Rh4(CO)12
Butterfly 4 31 62 2−
Re4(CO)16
Square plane 4 32 64 Pt4(O2CMe)8
Trigonal bipyramid 5 36 72 Os5(CO)16
Square pyramid 5 37 74 Fe5(CO)15C
Bicapped tetrahedron 6 42 84 Os6(CO)18
Octahedron 6 43 86 Ru6(CO)17C
Capped square pyramid 6 43 86 Os6(CO)18H2
Trigonal prism 6 45 90 Rh6(CO)15C3-
Capped octahedron 7 49 98 3−
Rh7(CO)16

Table 8.6:Metallaboranes and Metallacarboranes with Closo Structures:

No of skeletal atom Shape Examples
Octahedron
6 B4H6(CoCp)2 C2B3H5Fe(CO)3
Pentagonal Bipyramid
7 C2B4H6Ni(PPh3)2 C2B3H5 (CoCp)2
Dodecahedron
8 C2B4H4[(CH3)2Sn]CoCp
Capped square antiprism
9 C2B6H8Pt(PMe3)2 C2B5H7(CoCp)2
Bicapped square antiprism
10 [B9H9NiCp]- CB7H8(CoCp)NiCp)
Octahedron
11 [CB9H10CoCp]- C2B8H10IrH(PPh3)2
Icosahedron
12 C2B7H9(CoCp)3 C2B9H11Ru(Co)3

To do this, two additional electrons must be added to the tetrahedron to keep all electrons paired.
In fact, this is a general principle:

• Adding electrons to a closo complex opens the structure, converting it to one of lower symmetry.
• The butterfly structure results when an edge is removed from the tetrahedron.
• If we add two electrons to the butterfly structure, another edge is lengthened (another bond broken) and we end up
with a square plane.
As you become more familiar with transition metal clusters (no nonmetals in the framework) you will come to associate closo
structures with numbers of electrons.A trimer will have 48 electrons, a tetrahedron will have 60 electrons, a trigonal bipyramid
will have 72 electrons, and an octahedron will have 86. Some care is required, however, as can be illustrated with Os 3H2(CO)10.
An electron count gives us 46 electrons rather than 48. If, however, we allow for one Os - Os double bond, the electron count is
as expected. In accord with this expectation, one osmium-osmium bond is found to be shorter than the other two and the
complex shows the reactivity expected for an unsaturated complex.Some of the beautiful relationships that exist between closo,
nido, and arachno osmium complexes are shown in Figure.
Fig 8.3: Structures of Osmium complexes which have seven pairs of skeletal electrons.

Each capped triangular face adds twelve electrons to the total electron count, but the number of skeletal pairs remains seven.
Likewise removing Os(CO)3 deletes twelve electrons without changing the number of skeletal pairs. The diagonal lines show
alternate geometries with the same total number of electrons.
QUESTIONS:
1. The compound which obeys 18-electron rule is:
(a) Mn(CO) (b) Fe(CO)4
(c) V(CO)6 (d) Cr(CO)6
Solution: [Cr(CO)6]
TVE=6 + 6 x 2 = 6 + 12 = 18
Answer: (d)
2. The complex which obeys the 18 electron rule is

(a) Fe(CO)4 (b) Ni(CO)3(PPh3)
(c) Cr(CO)5 (d) Cr(C5H5)2
Solution: Ni(CO)3(PPh3)
TVE = 10 + 3 x 2 + 2 = 18
Answer: (b)
3. The bonding of cyclopentadienyl in Ti(Cp)4 is such that

(a) all Cp rings are pentahapto
(b) one Cp ring is pentahapto and other three rings are monohapto
(c) two Cp rings monohapto and the other two rings are pentahapto
(d) All Cp rings are monohapto
Solution:
Structure of: Ti(CP)4→ d0 follows 16 electron rule
TVE = 4 + 2 x 1 + 2 x 5 = 16
Answer: (c)
4. Which of the following complex show 18 electron system

(i) [(C6H6)2Cr] (ii) [HMn(CO)5],
(iii) [(CH3CO)Rh(CO)I3]-, (iv) [CpFe(CO)2 (CH3)],
Correct option is:
(a) iii only (b) I, ii and iv
(c) i and iv (d) ii only
Answer: (b)
5. The neutral complex which follows the 18-electron rule is :

(a) (η5–C5H5)Fe(CO)2 (b) (η5-C5H5)Mo(CO)3
(c) (η5–C 5H5)2CO (d) (η5C5H5)Re(η6 -C6H6)
Solution:
(η5–C5H5)Re(η6-C6H6)
TVE = 5 + 7 + 6 = 18
Answer: (d)

6. Find oxidation state of the following compounds?

(a) PdCl2 (b) Pd(PPh3)4
(c) Pd(OAc)2 (d) Pd(Br)Ph
Solution:
(a) PdCl2 (b) Pd(PPh3)4
x -2 = 0, x = 2 x+0 = 0, x = 0
Oxidation state = + 2 Oxidation state = 0
(c) Pd(OAc)2 (d) Pd(Br)Ph

x+2(-1) =O, x = 2 x-1-1 = 0, x = 2
Oxidation state= + 2 Oxidation state = + 2
7. On the basis of18 electron rule, find out the value of n.

(i) TcBr(CO)n (ii) Na2[Fe(Co)n]
(iii) [Mn(CO)n]- (iv) [IrC12 (CS)n (PPh3)2(H)]
(v) [Rh(CO)3]n
Solution:
(i) TcBr(CO)n
7 + 1 + 2n= 18
n=5
(ii) Na2 [Fe(CO)n]

8 + 2 + 2n = 18, 2n = 8
n=4
(iii) [Mn(CO)n]-
7 + 2n + 1= 18, 2n= 10 = 5
(iv) [IrCl2 (CS)n (PPh3)2(H)]

9 + 2 + 4 + 1 + 2n = 18, 2n = 18 - 16
n=l
(v) [Rh(CO)3]n
6+9+n=18 or n=18-15 or n=3
8. Based on isolobalanalogies , choose the groups that might replace the group in boldface in
(a) Co3 (CO)9CH→ OCH3 , N(CH3)2 , or SiCH3 ?
Solution:
• Isolobal groups have the same number, shape and valence orbitals and the same number of electrons in those
orbitals.The CH group has three sp3 hybrid orbitals that each contain a single electron.
• The SiCH3 group has three similar orbitals similarly occupied, so it is isolobal with CH and would probably replace
it in Co3(CO)9CH to form Co3(CO)9SiCH3 . In contrast, the OCH3 and N(CH3)2 groups are not isolobal with CH .
Instead, they have, respectively, three sp3 orbitals that each contain a pair of electrons and two sp3 orbital that
each contain a pair of electrons.

(b) (OC)5MnMn(CO)5→ I , CH2 or CCH3 ?
Solution:
• The Mn(CO)5 group has a single 𝜎 - type orbital that contains a single electron . An iodine atom is isolobal with it,
since it also has a singly occupied 𝜎 orbital. Therefore, you can expect the compound MnI(CO) 5 to be reasonably
stable . In contrast, the CH2 and CCH3 are not isolobal with Mn(CO)5.The CH2 group has either a doubly occupied 𝜎
orbital and an empty 𝑝 orbital or singly occupied 𝜎 orbital and a singly occupied 𝑝 orbital.
• The CCH3 group has three singly occupied 𝜎 orbitals (note that it is isolobal with SiCH3.
9. Ligand substitution reactions on metal clusters are often found to occur by associative mechanism , and it is postulated that
these occur by initial breaking of an M-M bond , thereby providing an open coordination site for the incoming ligand. If the
proposed mechanism is applicable, which would you expect to undergo the fastest exchange with added 13CO , Co4(CO)12
or Ir4(CO)12? Suggest an explanation.
Solution:
• If the rate –determining step in the substitution is cleavage of one of the metal – metal bonds in the cluster.
• The cobalt complex will exhibit faster exchange .
• This is because metal – metal bond strengths increase down a group in the d-block.
• Therefore, Co-Co bonds are weaker than Ir – Ir bonds , all other things like geometry and ligand types kept the
same .

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Index

Chapter 1 Introduction to Coordination Chemistry

Chapter 2 Isomerism of the coordination compounds

Chapter 3 Theories of coordination chemistry

Chapter 4 Term symbol and electronic spectra of the coordination compounds

Chapter 6 Stability and the reaction mechanism of the coordination complexes

Chapter 8 Interaction of metal with carbonyl & nitrosyl ligand

Chapter 9 Reactions of the organometallic compounds & metal carbenes

Chapter 10 New Generation Of Organometallic Chemistry : Metallocene Compounds

Chapter 11 Applications of organometallic compounds: homogeneous catalysis

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8.1.1. Low Nuclearity Carbonyl Clusters (LNCC):

Calculation of number of M-M bonds using 18/16-electron rule in LNCC:

Therefore, in Mn2 (Co)10 only one M-M bonds is present.

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b. Co2(CO)8 - valence electron count

c. Fe2(Co)9 - valence electron count

d. M3(CO)12 M= Fe, Ru, Os

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Out of 3 metals, 2 metals Co-ordination number = 7 And one Co-ordination number = 6

Solution Co4(CO)12 :- Bridged CO = 9

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To Determine the Unknown Quantity Using 18-Electron Rule:

b. [(ƞ5- C5H5)Mn(CO)x]2 (Mn = Mn double bond)

c. [(ƞ5 – C5H5)3Ni3(µ3 - CO)2]x (Three Ni-Ni bonds)

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To Identify the Transition Metal in a Complex Using 18-Electron Rule:

c. [M (µ3 -C5H5) (CO) 5] (M is 3d-series transition metal)

8.1.2. High Nuclearity Carbonyl Clusters:

Based on wade’s rules:

The Number of vertices = S – 1

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Structure Boranes Transition Metal Clusters

High nuclear metal carbonyl clusters

a. Rh6(Co)16 :- Total valence electron count(TEC)

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8.2. Zintl Ions

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Tetrahedral Trigonal Capped Trigonal

8.3. Isolobal Species

These are proposed by hofmann

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Cl + e-→ Cl- 8e-

Mn(Co)5 + e-→ [ Mn (Co)5]-

Isolobal analogy of transition metal cluster and Boranes:

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Skeletol e- pairs (or) Frame work e- pair for higher boranes:

→ B2H6 – Nido – n + 2 = 2 + 2 = 4 pairs = 8e-

→ B4H10 – Arachno – n + 3 = 4 + 3 = 7 pairs = 14e-

→ B5H9 – Nido – n + 2 = 5 + 2 = 7 pairs = 14e-

→ B5H11– Arachno – n + 3 = 5 + 3 = 8 pairs = 16e-s

→ B6H10 – Nido – n + 2 = 6 + 2 = 8 pairs = 16e-

→ B10H14 – Nido – n + 2 = 10 + 2 = 12 pairs = 24e-

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• Calculation of different types of bonding in higher boranes: