Phosphane lone-pair energies as a measure of ligand donor strengths and relation to activation energies

H. M. Senn; D. V. Deubel; P. E. Blöchl; A. Togni; G. Frenking

doi:10.1016/S0166-1280(00)00415-2

Phosphane lone-pair energies as a measure of ligand donor strengths and relation to activation energies

H. M. Senn, D. V. Deubel, P. E. Blöchl, A. Togni, G. Frenking

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

Using density-functional theory as implemented in the projector- augmented wave method, we have calculated structures, energy levels, structures of the protonated forms, and proton affinities of the phosphanes PH₃, PF₃, P(CF₃)₃, PMe₃, P(NMe₂)₃, P(C₆H₅)₃, P(p-C₆H₄OMe₂)₃, and P(p-C₆H₄NMe₂)₃. The donor strengths of the phosphanes are discussed in terms of lone-pair energies and proton affinities. The influence of the donor ability of the phosphane ligands on the protonolytic cleavage of the metal-carbon bond in [NiCl(CH₂CH₂NH₃)(PR₃)₂]⁺ complexes has been studied. A linear relationship between the lone-pair energies of the phosphanes and the activation barrier has been established. (C) 2000 Elsevier Science B.V.

Original language	English
Pages (from-to)	233-242
Number of pages	10
Journal	Journal of Molecular Structure: THEOCHEM
Volume	506
Issue number	1-3
DOIs	https://doi.org/10.1016/S0166-1280(00)00415-2
State	Published - 14 Jul 2000
Externally published	Yes

Keywords

Ab initio molecular-dynamics calculations
Density-functional calculations
Homogeneous catalysis
Phosphanes
Transition states

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10.1016/S0166-1280(00)00415-2

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title = "Phosphane lone-pair energies as a measure of ligand donor strengths and relation to activation energies",

abstract = "Using density-functional theory as implemented in the projector- augmented wave method, we have calculated structures, energy levels, structures of the protonated forms, and proton affinities of the phosphanes PH3, PF3, P(CF3)3, PMe3, P(NMe2)3, P(C6H5)3, P(p-C6H4OMe2)3, and P(p-C6H4NMe2)3. The donor strengths of the phosphanes are discussed in terms of lone-pair energies and proton affinities. The influence of the donor ability of the phosphane ligands on the protonolytic cleavage of the metal-carbon bond in [NiCl(CH2CH2NH3)(PR3)2]+ complexes has been studied. A linear relationship between the lone-pair energies of the phosphanes and the activation barrier has been established. (C) 2000 Elsevier Science B.V.",

keywords = "Ab initio molecular-dynamics calculations, Density-functional calculations, Homogeneous catalysis, Phosphanes, Transition states",

author = "Senn, {H. M.} and Deubel, {D. V.} and Bl{\"o}chl, {P. E.} and A. Togni and G. Frenking",

year = "2000",

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doi = "10.1016/S0166-1280(00)00415-2",

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T1 - Phosphane lone-pair energies as a measure of ligand donor strengths and relation to activation energies

AU - Senn, H. M.

AU - Deubel, D. V.

AU - Blöchl, P. E.

AU - Togni, A.

AU - Frenking, G.

PY - 2000/7/14

Y1 - 2000/7/14

N2 - Using density-functional theory as implemented in the projector- augmented wave method, we have calculated structures, energy levels, structures of the protonated forms, and proton affinities of the phosphanes PH3, PF3, P(CF3)3, PMe3, P(NMe2)3, P(C6H5)3, P(p-C6H4OMe2)3, and P(p-C6H4NMe2)3. The donor strengths of the phosphanes are discussed in terms of lone-pair energies and proton affinities. The influence of the donor ability of the phosphane ligands on the protonolytic cleavage of the metal-carbon bond in [NiCl(CH2CH2NH3)(PR3)2]+ complexes has been studied. A linear relationship between the lone-pair energies of the phosphanes and the activation barrier has been established. (C) 2000 Elsevier Science B.V.

AB - Using density-functional theory as implemented in the projector- augmented wave method, we have calculated structures, energy levels, structures of the protonated forms, and proton affinities of the phosphanes PH3, PF3, P(CF3)3, PMe3, P(NMe2)3, P(C6H5)3, P(p-C6H4OMe2)3, and P(p-C6H4NMe2)3. The donor strengths of the phosphanes are discussed in terms of lone-pair energies and proton affinities. The influence of the donor ability of the phosphane ligands on the protonolytic cleavage of the metal-carbon bond in [NiCl(CH2CH2NH3)(PR3)2]+ complexes has been studied. A linear relationship between the lone-pair energies of the phosphanes and the activation barrier has been established. (C) 2000 Elsevier Science B.V.

KW - Ab initio molecular-dynamics calculations

KW - Density-functional calculations

KW - Homogeneous catalysis

KW - Phosphanes

KW - Transition states

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U2 - 10.1016/S0166-1280(00)00415-2

DO - 10.1016/S0166-1280(00)00415-2

M3 - 文章

AN - SCOPUS:0034647990

SN - 0166-1280

VL - 506

SP - 233

EP - 242

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

IS - 1-3

ER -

Phosphane lone-pair energies as a measure of ligand donor strengths and relation to activation energies

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Keywords

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