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Example:
LnM CO 18 e LnM 16 e + CO L' LnM L' 18 e
18-e oct
11/5/2013
16-e SP
Ligand Substitution and Activation
distorted TBP
2
L'
LnM L' 18 e
-L
Ln-1M L' 16 e
(cis-platin !)
L2M(Cl)(H2O)+
11/5/2013 Ligand Substitution and Activation 3
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
11/5/2013
M 1-e
M 5-e 3-e
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.
11/5/2013 Ligand Substitution and Activation 5
Fe(CO)4L
Fe(CO)5
CO
Fe(CO)4
Fe(CO)5
Fe(CO)4L
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
N Rh N N
H+ S
N S Rh N N
11/5/2013
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
+ H+
Ni
Ni
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13
11/5/2013
14
MeOH
HI
MeCOOH
MeI
H2O
MeCOI
Rh(CO)2I3Me
Rh(CO)2I3(COMe)
insertion CO
11/5/2013 Ligand Substitution and Activation 15
11/5/2013
16
Nucleophilic abstraction
Na+ NaH Cr OC OC CO OC OC Cr CO
Cp2WH2
BuLi
Cp2WH
Li
11/5/2013
17
Nucleophilic addition
OH (H2O)Cl2Pd + OH(H2O)Cl2Pd
11/5/2013
18
Cl Cl Pd
2Cl Cl
Cl H2O Pd CH3CHO
- ClCl H2O Pd OH
Cl H2O Pd
-H elim OH H
11/5/2013
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
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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21
OD diss
D2O
O CH2D H O CH3
22
diss