Abstract
| Original language | English |
|---|---|
| Pages (from-to) | 16728-16733 |
| Number of pages | 6 |
| Journal | Chemistry - A European Journal |
| Volume | 23 |
| Issue number | 66 |
| Early online date | 20 Nov 2017 |
| DOIs | |
| Publication status | Published - 27 Nov 2017 |
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Keywords
- density fuctional calculations
- homogenous catalysis
- nickel
- electron transfer
- ligand effects
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Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3-n))4]. / Funes-Ardoiz, Ignacio; Nelson, David J.; Maseras, Feliu.
In: Chemistry - A European Journal, Vol. 23, No. 66, 27.11.2017, p. 16728-16733.Research output: Contribution to journal › Article
TY - JOUR
T1 - Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3-n))4]
AU - Funes-Ardoiz, Ignacio
AU - Nelson, David J.
AU - Maseras, Feliu
PY - 2017/11/27
Y1 - 2017/11/27
N2 - Density functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMenPh(3-n))4], revealing the crucial role of an open shell singlet transition state for halide abstraction. The formation of NiI versus NiII has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMenPh(3-n))3], via an open shell singlet transition state; (ii) SN2-type oxidative addition to [Ni(PMenPh(3-n))3], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMenPh(3-n))2]. For the case of [Ni(PMe3)4], a microkinetic model was used to show that these data are consistent with the experimentally-observed ratios of NiI and NiII. Importantly, [Ni(PMenPh(3-n))2] complexes often have little if any role in the oxidative addition reaction because they are relatively high in energy. The behaviour of [Ni(PR3)4] complexes in catalysis is therefore likely to differ considerably from those based on diphosphine ligands in which two coordinate Ni0 complexes are the key species undergoing oxidative addition.
AB - Density functional theory (DFT) calculations have been used to study the oxidative addition of aryl halides to complexes of the type [Ni(PMenPh(3-n))4], revealing the crucial role of an open shell singlet transition state for halide abstraction. The formation of NiI versus NiII has been rationalised through the study of three different pathways: (i) halide abstraction by [Ni(PMenPh(3-n))3], via an open shell singlet transition state; (ii) SN2-type oxidative addition to [Ni(PMenPh(3-n))3], followed by phosphine dissociation; and (iii) oxidative addition to [Ni(PMenPh(3-n))2]. For the case of [Ni(PMe3)4], a microkinetic model was used to show that these data are consistent with the experimentally-observed ratios of NiI and NiII. Importantly, [Ni(PMenPh(3-n))2] complexes often have little if any role in the oxidative addition reaction because they are relatively high in energy. The behaviour of [Ni(PR3)4] complexes in catalysis is therefore likely to differ considerably from those based on diphosphine ligands in which two coordinate Ni0 complexes are the key species undergoing oxidative addition.
KW - density fuctional calculations
KW - homogenous catalysis
KW - nickel
KW - electron transfer
KW - ligand effects
UR - http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-3765
U2 - 10.1002/chem.201702331
DO - 10.1002/chem.201702331
M3 - Article
VL - 23
SP - 16728
EP - 16733
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 66
ER -