Ligand substitution reactions: dissociative

Example:
LnM CO 18 e LnM 16 e + CO L' LnM L' 18 e

Factors influencing ease of dissociation:

1e row < 2e row > 3e row d8-ML5 > d10-ML4 > d6-ML6 stable ligands (CO, olefins, Cl-) dissociate easily (as opposed to e.g. CH3, Cp).
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Dissociative substitution in ML6

16-e ML5 complexes are usually fluxional; the reaction proceeds with partial inversion, partial retention of stereochemistry.
or

18-e oct
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16-e SP
Ligand Substitution and Activation

distorted TBP
2

Ligand substitution reactions: associative

Example:
LnM 16 e
Br- Cl-

L'

LnM L' 18 e

-L

Ln-1M L' 16 e

Sometimes the solvent is involved:

L2MCl2 L2M(Cl)(Br) Br- - H O 2
H2O - Cl

(cis-platin !)

L2M(Cl)(H2O)+
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Ligand rearrangement
Several ligands can switch between n-e and (n-2)-e situations, thus enabling associative reactions:
M N O 3-e M N 1-e O CO M R (1+2)-e
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M 1-e

M 5-e 3-e

Ligand Substitution and Activation

Ligand substitution reactions: redox-induced

LnM + L' LnM L'

For 17-e 19-e usually fast equilibrium: Reduction promotes dissociative substitution. Oxidation promotes associative substitution. In favourable cases, the product oxidizes/reduces the starting material redox catalysis.
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Fe(CO)4L

Fe(CO)5

CO

Fe(CO)4

Fe(CO)5

Fe(CO)4L

Initiation by added reductant.

Sometimes, radical abstraction produces a 17-e species (see C103).

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Ligand substitution reactions: photochemical

Visible light can excite an electron from an M-L bonding orbital to an M-L antibonding orbital (LF transition). This results in fast ligand dissociation.
M(CO)6 d h d

Requirement: the complex must absorb, so it must have a colour.

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Some ligands have a low-lying * orbital and undergo MLCT excitation. This leads to easy associative substitution.
The excited state is formally (n-1)-e !
M(CO)4(phen) d d * h

M-M bonds dissociate easily on irradiation

(n-1)-e associative substitution
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Ligand activation: electrophilic and nucleophilic attack

Electron-rich metal fragment: ligands activated for electrophilic attack.
+ ++

N Rh N N

H+ S

N S Rh N N

N4: strong -donor

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Ligand activation: electrophilic and nucleophilic attack

Electron-poor metal fragment: ligands activated for nucleophilic attack.
Bu BuLi Cr OC OC CO OC OC Cr CO H Li+

CO: strong -acceptor

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Electrophilic attack on ligand

Hapticity may increase or decrease. Formal oxidation state of metal may increase. +
MI H+ MI + M(0) H+ MII

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Ligand Substitution and Activation

11

Electrophilic addition
O Et3O+ Fe(CO)3 OEt

Fe(CO)3
+ + MeB(C6F5)3Me 14 e

Electrophilic abstraction
Me Cp2Zr Me 16 e B(C6F5)3 Cp2Zr

Alkyl exchange also starts with electrophilic attack.

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Competition: attack of electrophile on metal

(may be followed by shift to ligand)
+ Fe H+ Fe H

+ H+

Ni

Ni

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Ligand Substitution and Activation

13

Electrophilic attack on metal

Can be the start of oxidative addition
I2(CO)2Rh Me I I2(CO)2RhMe + II3(CO)2RhMe

Key reaction in the Monsanto acetic acid process:

HI MeOH + CO MeCOOH "Rh"

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Ligand Substitution and Activation

14

MeOH

HI

MeCOOH

MeI

H2O

MeCOI

Rh(CO)2I2 oxidative addition reductive elimination

Rh(CO)2I3Me

Rh(CO)2I3(COMe)

insertion CO
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Nucleophilic attack on ligand

Nucleophile "substitutes" metal
hapticity usually decreases

Oxidation state mostly unchanged Competition: nucleophilic attack on metal

usually leads to substitution

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Ligand Substitution and Activation

16

Nucleophilic abstraction
Na+ NaH Cr OC OC CO OC OC Cr CO

Cp2WH2

BuLi

Cp2WH

Li

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Ligand Substitution and Activation

17

Nucleophilic addition
OH (H2O)Cl2Pd + OH(H2O)Cl2Pd

Key reaction of the Wacker process:

C2H4 + O2 PdCl2, H2O CuCl2 CH3CHO

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Ligand Substitution and Activation

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Cl Cl Pd

2Cl Cl

C2H4 Cl Cl Pd H2O Cl Cl H2O Pd Cl OH Cl

OHPd(0) + H+ + H2O + 2 Cl- 2 e (CuCl2 CuCl) H Cl Cl H2O Pd

Cl H2O Pd CH3CHO

- ClCl H2O Pd OH

ClCl H2O Pd O H Cl -H elim H2O Pd OH ins

Cl H2O Pd

-H elim OH H

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Ligand Substitution and Activation

19

How can you distinguish between internal and external attack of OH- ? Cl Cl
H2O Pd
-

OH

OH-

Cl
-

H2O

Pd

Cl

OH

- Cl

??
ins Cl H2O Pd H O -

Cl H2O Pd OH

Use trans-CHD=CHD and trap the intermediate Pd-C-C-OH with CO: OH

Cl H2O Pd Cl CO - ClPd CO ins HO O O
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OH

nucl attack

Pd O
20

D OH D Pd D OHHO Pd D Pd D D Pd

HO D D HO Pd D D CO O O D O CO O D D D

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Ligand Substitution and Activation

21

Could acetaldehyde be formed directly as vinyl alcohol ?

Perform reaction in D2O:
OD Pd H ins OD Pd -H elim Pd D
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OD diss

D2O

O CH2D H O CH3
22

diss