Can bis(imino)pyridine iron, (PDI)FeL1L2, complexes catalyze CH bond functionalization?Electronic supplementary information (ESI) available: (1) Complete reaction profile for the CH functionalization reaction (1) and the competing homocoupling reaction catalyzed by complex 3; CH2N2 is employed as carbene precursor. (2) Complete reaction profile for the CH functionalization reaction (1) and several competing reactions (including diazo coupling) catalyzed by 4; CH2N2 is employed as carbene precurs
The DFT approach is used to analyse the mechanism and controlling factors of (PDI)Fe II (N 2 ) 2 and (PDI)Fe II Cl(OEt 2 ) complexes ( i.e. a combination of a earth-abundant metal (Fe) and a non-innocent bis(imino)pyridine (PDI) ligand) catalyzed benzylic CH bond functionalization by unsubstituted a...
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| Main Authors | , |
|---|---|
| Format | Journal Article |
| Language | English |
| Published |
29.07.2013
|
| Online Access | Get full text |
| ISSN | 2041-6520 2041-6539 |
| DOI | 10.1039/c3sc51723c |
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| Summary: | The DFT approach is used to analyse the mechanism and controlling factors of (PDI)Fe
II
(N
2
)
2
and (PDI)Fe
II
Cl(OEt
2
) complexes (
i.e.
a combination of a earth-abundant metal (Fe) and a non-innocent bis(imino)pyridine (PDI) ligand) catalyzed benzylic CH bond functionalization by unsubstituted and donoracceptor diazocarbenes. Results suggest that the use of (PDI)FeCl(OEt
2
) complex and donoracceptor carbenes is absolutely necessary for the benzylic CH bond alkylation. Furthermore, the non-innocent PDI ligand acts as a one-electron oxidant upon formation of the reactive (PDI)Fe(Cl)CR
1
R
2
carbenoid.
Can the bis(imino)pyridine iron, (PDI)FeL
1
L
2
, complexes catalyze CH bond functionalization? |
|---|---|
| Bibliography: | is employed as carbene precursor. (3) Key steps of the reaction (1). Here we present energies G H Electronic supplementary information (ESI) available: (1) Complete reaction profile for the CH functionalization reaction (1) and the competing homocoupling reaction catalyzed by complex N is employed as carbene precursor. (7) Absolute energies of the structures involved in the CH functionalization reaction (1) and related competing processes catalyzed by in kcal mol sol is employed as carbene precursor. (8) Absolute energies of the structures involved in the CH functionalization reaction (1) and related competing processes catalyzed by 14_DA and is employed as carbene precursor. (5) Main resonance structures contributing to the carbenoids carbene precursor. (4) Complete reaction profile for the CH functionalization reaction (1) and several competing reaction (including diazo coupling) catalyzed by 14 15 is employed as carbene precursor. (10) Calculated cartesian coordinates (in ) of all reported structures in this paper. See DOI CH and alkyl complexes the donoracceptor CPh(COH)N ( 10.1039/c3sc51723c ) and schematic structures of the reactants, intermediates and products of the reactions (1b) and (1c) utilizing the model complex is employed as carbene precursor. (2) Complete reaction profile for the CH functionalization reaction (1) and several competing reactions (including diazo coupling) catalyzed by 1 2 presented in this paper. (6) Absolute energies of the structures involved in the CH functionalization reaction (1) and related competing processes catalyzed by 3 15_DA 4 and the donoracceptor (DA) CPh(COH)N is employed as carbene precursor. (9) Absolute energies of the structures involved in the CH functionalization reaction (1) and related competing processes catalyzed by |
| ISSN: | 2041-6520 2041-6539 |
| DOI: | 10.1039/c3sc51723c |