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Formalisms – Oxidation State & Electron Counting

Understanding the nature of the metal center is critical in understanding how it reacts.

There are four things we need to know:

(1) The oxidation state of the metal (2) The number of d electrons on the metal in that oxidation state (3) The coordination number of the metal (4) The availability (or lack thereof) of any coordination sites on the metal

Oxidation State – The charge left on the metal after all ligands have been removed in their normal, closed shell, configuration.

There are two ways to figure out the oxidation state. The one we will use involves breaking the metal–ligand bonds heterolytically with both electrons going with the ligand.

Examples:

M Cl M (+1) M PPh M 3 (0) OR M M R (0)
M
Cl
M
(+1)
M
PPh
M
3
(0)
OR
M
M
R (0)
Cl PPh 3
Cl
PPh 3

OR

M (+1) M PPh M 3 (0) OR M M R (0) Cl PPh 3 OR

R

M H
M
H

M

M H

M

M H

H

M H

(+1)

 
M

M

M
M

(+1)

M CO H H M H H
M
CO
H
H
M
H
H

M

(0)

M

(0)

CO H H
CO
H
H

H

H

Formalisms – Oxidation State & Electron Counting Now that we know the oxidation state of
Formalisms – Oxidation State & Electron Counting Now that we know the oxidation state of

Formalisms – Oxidation State & Electron Counting

Now that we know the oxidation state of the metal we can figure out the d -electron count. This can be done easily by consulting the periodic table.

The 4s and 3d orbitals are very close in energy and for complexes of transition metals it is a good approximation that the d orbitals are filled first.

 

Group #

4

5

6

7

8

9

10

11

 

First row

3d

Ti

V

Cr

Mn

Fe

Co

Ni

Cu

Second row

4d

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Ag

Third row

5d

Hf

Ta

W

Re

Os

Ir

Pt

Au

 

0

4

5

6

7

8

9

10

I

3

4

5

6

7

8

9

10

 

oxidation

 

state

II

2

3

4

5

6

7

8

9

 

III

1

2

3

4

5

6

7

8

IV

0

1

2

3

4

5

6

7

 
 
 

# of d -electrons

 
2 3 4 5 6 7 8 IV 0 1 2 3 4 5 6 7
2 3 4 5 6 7 8 IV 0 1 2 3 4 5 6 7

Formalisms – Oxidation State & Electron Counting

Why is knowing the number of d-electrons important?

18 electron rule – In mononuclear diamagnetic complexes, the toal number of electrons in the bonding shell (the sum of the metal d electrons plus those contributed by the ligands) never exceeds 18. This determines the maximum number of ligands allowable for any metal in any oxidation state.

If a metal complex has 18 electrons in the bonding shell it is coordinatively saturated.

If a metal complex has fewer than 18 electrons it is coordinatively unsaturated and typically has at least one vacant coordination site.

In general, catalytic processes require the metal catalyst to have a vacant coordination site so that the substrate can bind.

Knowing the oxidation state of the metal and the number of d electrons is only part of the story. In order to properly count the electrons in the bonding shell we also need to know how many electrons each ligand supplies. It is not always two.

Formalisms – Oxidation State & Electron Counting

Classes of ligands – There are three classes of ligands: (1) formal anions (X-Type); (2) formal neutrals (L-Type); (3) formal cations.

All of these ligand classes have one pair of electrons for bonding the metal that are used to determine the metal's oxidation state. Often the ligand will also contain additional unsaturation that can donate addition electron pairs to the bonding shell. The manner in which these unsaturated ligands binds is called the "hapticity" ( η ).

Some Simple X-Type Donors – monohapto ( η 1 ); only donate two electrons to bonding shell

alkyl

acyl

aryl); only donate two electrons to bonding shell alkyl acyl O C R Ar hydride  

O

C R CR

Ar
Ar

hydride

 

H

H

H

alkenyl

 

H

H
H

halide

X
X

alkynyl

  H H alkenyl   H H halide X alkynyl R cyanide C N Allyl –

R

cyanide

H H alkenyl   H H halide X alkynyl R cyanide C N Allyl – X-Type

H H alkenyl   H H halide X alkynyl R cyanide C N Allyl – X-Type

CN

H alkenyl   H H halide X alkynyl R cyanide C N Allyl – X-Type ligand
H alkenyl   H H halide X alkynyl R cyanide C N Allyl – X-Type ligand

Allyl – X-Type ligand with multiple coordination modes; can donate 2 or 4 electrons

multiple coordination modes; can donate 2 or 4 electrons η 1 M 2e – ( σ

η

1

M

2e ( σ ) 1 coordination site

M

4 electrons η 1 M 2e – ( σ ) 1 coordination site M η 3

η

3

4e ( π ) 2 coordination sites

1 coordination site M η 3 4e – ( π ) 2 coordination sites M η

M

η

3

4e ( σ , π ) 2 coordination sites

Formalisms – Oxidation State & Electron Counting

Cyclopentadienyl – X-Type ligand with multiple coordination modes; can donate 2, 4, or 6 electrons

multiple coordination modes; can donate 2, 4, or 6 electrons η 1 M 2e – 1

η

1

M

2e 1 coordination site

2, 4, or 6 electrons η 1 M 2e – 1 coordination site M η 3

M

η

3

4e 2 coordination sites

1 coordination site M η 3 4e – 2 coordination sites M η 5 6e –

M

η

5

6e 3 coordination site (most common)

Some common L-Type ligands and their hapticity

phosphine

amine

nitrile

carbonyl

carbene

R

R

3

P

3 N

RCN

OC

X

amine nitrile carbonyl carbene R R 3 P 3 N RCN OC X R M η

R

M

η 1

2e

M

η 1

2e

M

η 1

2e

M

η 1

2e

M

η 1

2e

alkene/alkyne

alkene/alkyne M M η 2 2e –

M

alkene/alkyne M M η 2 2e –

M

η 2

2e

diene

diene M η 4 4e –

M

η 4

4e

arene

arene η 6 6e –

η 6

6e

M

Note: For polydentate ligands, count each attachment separately.

Carbene Complexes

Several types are known. How they contributes to the overall electron counting is dependent on the subtituents and metal involved.

Fischer carbenes

L

n M

XR 1

and metal involved. Fischer carbenes L n M XR 1 R 2 X = O, NR,

R 2

X = O, NR, S M = low-valent, middle or late transition metals

• L-type ligand

• donating 2 electrons

Schrock carbenes

L

n M

R

1

• donating 2 electrons Schrock carbenes L n M R 1 R 2 R 1 ,

R

2

R 1 , R 2 = alkyl or H M = high-valent carbyl or middle transition metals

• 2X-type ligand (–2 charge)

• donating 4 electrons

Carbenoids R 1 L n M
Carbenoids
R 1
L n M

EWG

L n M = Rh 2 (O 2 CR) 4 , N 4 Ru, (N 2 O 2 )Ru, or (N,N)Cu

• L-type ligand

• donating 2 electrons

Vinylidenes R 1 L n M C
Vinylidenes
R
1
L n M
C

R

2

R 1 , R 2 = alkyl, aryl, or H

• L-type ligand

• donating 2 electrons

N -Heterocyclic carbenes

L n M

R

N N
N
N

R

R = alkyl or aryl

• generally a spectator ligand

• L-type ligand

• donating 2 electrons

Formalisms – Oxidation State & Electron Counting

Examples – For each complex determine the oxidation state of the metal, the number of d electrons supplied by the metal, the overall electron count, and the number of vacant coordination sites.

Ph

Ph

3 P

3 P

Rh PPh 3 3

of vacant coordination sites. Ph Ph 3 P 3 P Rh PPh 3 C l Wilkinson's

C l Cl

coordination sites. Ph Ph 3 P 3 P Rh PPh 3 C l Wilkinson's catalyst Pd

Wilkinson's

catalyst

Pd PPh 3

Ph

Ph 3 P PPh 3

3 P

catalyst Pd PPh 3 Ph Ph 3 P PPh 3 3 P M–M bonds: contribute 1e
catalyst Pd PPh 3 Ph Ph 3 P PPh 3 3 P M–M bonds: contribute 1e
catalyst Pd PPh 3 Ph Ph 3 P PPh 3 3 P M–M bonds: contribute 1e
catalyst Pd PPh 3 Ph Ph 3 P PPh 3 3 P M–M bonds: contribute 1e

M–M bonds: contribute 1e to each metal

Cr OC CO CO
Cr
OC
CO CO
Fe OC CO
Fe
OC
CO
CO OC CO OC Co Co CO OC CO OC
CO
OC
CO
OC
Co
Co
CO
OC
CO
OC
Fe OC
Fe
OC

CO

Zr
Zr

H

Cl Schwartz's
Cl
Schwartz's

reagent

d Orbitals and Ligand Bonding

The 18 electron rule is predicated on the notion that it is the d orbitals of the metal that are responsible for ligand binding as well as engaging the substrate in chemistry (the substrate can be thought of as nothing more than a particularly reactive ligand). Therefore understanding how the d orbitals of a metal interact with the sp hybrid orbitals of the ligand and/or substrate is important.

σ -donor bonds – formed by overlap of filled sp hybrid orbitals (or π -bonding orbitals) of ligand with vacant d orbitals of the metal. Orbital symmetry should be kept in mind.

M + one lobe of a vacant d orbital
M
+
one lobe of a
vacant d orbital
R R + P
R R
+
P

R

filled sp 3 orbital

Ligands that are primarily σ -donors (e.g., R 3 P, R 3 N, H and R ) increase electron density on the metal

What about unsaturated ligands?

d Orbitals and Ligand Bonding

π -Bonds on the ligand can also serve as a σ -donor ligands

BUT

the

M + one lobe of a vacant d orbital
M
+
one lobe of a
vacant d orbital
+ – + – filled π bond
+
+
filled π bond

π * orbital also has the same symmetry and similar energy to the d orbitals

– + M –+ – filled
– +
M
–+
filled

d orbital

+ – – + vacant π * orbitals
+
+
vacant
π * orbitals

By this model, the metal is donating electron density to the ligand. This is known as "back bonding" and can act as an electron sink. Thus the electron density of the metal will decrease .

d Orbitals and Ligand Bonding

Two different types of backbonding are possible depending on the geometry of the ligand orbitals.

longitudinal

vacant d orbital lone pair of CO serving as σ -donor – + + –
vacant
d orbital
lone pair of CO
serving as σ -donor
+
+ –
M
+
+
C
O
+
– +
filled metal
vacant CO
π * orbital

d orbital

perpendicular

vacant d orbital filled C=C π -bond as σ -donor + – – + +
vacant
d orbital
filled C=C
π -bond as
σ -donor
+
+
+ C
M
+
+ C
+
+
filled metal
d orbital
vacant C=C
π * orbital

Bottom Line

consequence its reactivity) can be tuned by varying the identity σ -donor ligands (add electron

density) and π -acceptor ligands (remove electron density).

because

of these two bonding modes the electron density of the metal (and as a

For this course I have chosen to focus more on the reactivity of metals rather than the structures. We will talk about ligand choices more when necessary.

Phosphine Ligands

Phosphine ligands are frequently used ligands for organometallic reactions. While they can be somewhat difficult to synthesize and are often oxygen sensitive, they are highly tunable. Influences on the metal can be mediated by electronics, cone angle, monodentate vs. bidentate, and bite angle.

Electronics: The identity of the substituents around the phosphorus atom has a profound influence on how donating the ligand is.

Me Me Me P trialkylphosphine
Me
Me
Me
P
trialkylphosphine
OR RO OR P phosphite
OR
RO
OR
P
phosphite
Ph Ph Ph P triarylphosphine
Ph
Ph
Ph
P
triarylphosphine
OR RO NR 2 P phosphoramidite
OR
RO
NR 2
P
phosphoramidite

ν co (cm -1 )

PR 3 P(t-Bu) 3

2056

PCy 3

2056

PMe 3

2064

P(C 6 H 4 -4-OMe) 3

2066

PPh 3

2069

P(OMe) 3

2079

P(OPh) 3

2085

ν co (cm -1 ) is determined with Ni(CO) 3 L and is a measurement of the amount of backbonding. More donating L, more backbonding and ν co decreases.

Cone Angle: This is a measure of the three-dimensional steric influence a ligand has on the enviroment around the metal. It can be changed idenpendently from electronics.

R R R P M cone angle ( Θ)
R
R
R
P
M
cone angle ( Θ)

PR 3

PH 3

θ

87

104

P(OMe) 3 107

PF

3

PMe 3

118

PMe 2 Ph

122

Ph 2 PCH 2 CH 2 PPh 2

123

PR 3

θ

PR 3

θ

PHPh 2

128

PPh(t-Bu) 2 170

P(OPh) 3

128

PCy 3

170

PEt 3

132

P(t-Bu) 3

182

PPh 3

145

PPh 3

145

PPh 2 (t-Bu) 157

P(o-tol) 3

194

Hartwig, Organotransition Metal Chemistry, 2010, pp 37–38.

Phosphine Ligands Bite Angle: This is a measure of the three-dimensional steric influence a ligand
Phosphine Ligands
Bite Angle: This is a measure of the three-dimensional steric influence a ligand has on the enviroment
around the metal. It can be changed idenpendently from electronics.
Ligand
Ligand
β n
β n
dppm (1, n = 1)
72
BISBI (5)
113 (92–155)
dppe (1, n = 2)
84 (70–95)
TRANSPHOS (6)
111
P
P
dppp (1, n = 3)
91
NORPHOS (7)
123 (110–145)
M
dppb (1, n = 4)
98
DPEphos (8)
102 (86–120)
bite angle ( β n )
DIOP (2)
102 (90–120)
DBFphos (9)
131 (117–147)
BINAP (3)
92
Xantphos (10)
112 (97–135)
Me-DuPHOS (4)
83
dppf (11)
96
Ph 2 P
PPh 2
n
1
O
O
P
P
O
PPh
2
PPh 2
PPh 2
PPh 2 10
PPh 2
PPh
2
8
O
2
4
Ph 2 P
6
PPh 2
PPh
2
Fe
PPh
2
O
PPh
2
Ph 2 P
PPh 2
PPh
PPh 2
2
9
11
Ph 2 P
PPh 2
PPh 2
7
3
5
Steinborn, Fundamentals of Organometallic Catalysis, 2012, pp 90.