A combined QM/MM study of ligand substitution enthalpies in the L2Fe(CO)3, RuCpL2Cl, and RuCp*L2Cl systems

Luigi Cavallo; Tom K. Woo; Tom Ziegler

doi:10.1139/v98-169

A combined QM/MM study of ligand substitution enthalpies in the L₂Fe(CO)₃, RuCpL₂Cl, and RuCp*L₂Cl systems

Luigi Cavallo, Tom K. Woo, Tom Ziegler^*

^*Corresponding author for this work

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

30 Scopus citations

Abstract

A combined density functional and molecular mechanics approach (QM/MM) has been validated in a study of the substitution reactions: (i) (PH₃)₂Fe(CO)₃ + 2ER₃ mutually implies (ER₃)₂Fe(CO)₃ + 2PH₃ (ER₃ = PMe₃, PEt₃, PMePh₂, PPh₃, PCyPh₂, P(i)Pr₃, PBz₃, PCy₃, AsEt₃, AsPh₃); and (ii) Cp'Ru(PH₃)₂Cl + 2ER3 mutually implies Cp'Ru(ER₃)₂Cl + 2PH₃ (Cp' = C₅H₅, C₅(CH₃)₅; ER₃ = PMe₃, PEt₃ P(n)Bu₃, PMe₂Ph, PMePh₂, PPh₃, AsEt₃, P(OMe)₃, P(OPh)₃, P(OCH₂)₃CEt). The steric influence of the R substituents on the substitution enthalpies correlates well with experimental data. The combined QM/MM approach is also able to afford molecular structures in good accord with experimental estimates.

Original language	English (US)
Pages (from-to)	1457-1466
Number of pages	10
Journal	Canadian Journal of Chemistry
Volume	76
Issue number	10
DOIs	https://doi.org/10.1139/v98-169
State	Published - 1998
Externally published	Yes

Keywords

Combined QM/MM
Ligand substitutions
Organometallic complexes

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

Access to Document

10.1139/v98-169

Cite this

@article{c417a0c459b647a58685f89fe01e3145,

title = "A combined QM/MM study of ligand substitution enthalpies in the L2Fe(CO)3, RuCpL2Cl, and RuCp*L2Cl systems",

abstract = "A combined density functional and molecular mechanics approach (QM/MM) has been validated in a study of the substitution reactions: (i) (PH3)2Fe(CO)3 + 2ER3 mutually implies (ER3)2Fe(CO)3 + 2PH3 (ER3 = PMe3, PEt3, PMePh2, PPh3, PCyPh2, P(i)Pr3, PBz3, PCy3, AsEt3, AsPh3); and (ii) Cp'Ru(PH3)2Cl + 2ER3 mutually implies Cp'Ru(ER3)2Cl + 2PH3 (Cp' = C5H5, C5(CH3)5; ER3 = PMe3, PEt3 P(n)Bu3, PMe2Ph, PMePh2, PPh3, AsEt3, P(OMe)3, P(OPh)3, P(OCH2)3CEt). The steric influence of the R substituents on the substitution enthalpies correlates well with experimental data. The combined QM/MM approach is also able to afford molecular structures in good accord with experimental estimates.",

keywords = "Combined QM/MM, Ligand substitutions, Organometallic complexes",

author = "Luigi Cavallo and Woo, {Tom K.} and Tom Ziegler",

year = "1998",

doi = "10.1139/v98-169",

language = "English (US)",

volume = "76",

pages = "1457--1466",

journal = "Canadian Journal of Chemistry",

issn = "0008-4042",

publisher = "National Research Council of Canada",

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T1 - A combined QM/MM study of ligand substitution enthalpies in the L2Fe(CO)3, RuCpL2Cl, and RuCp*L2Cl systems

AU - Cavallo, Luigi

AU - Woo, Tom K.

AU - Ziegler, Tom

PY - 1998

Y1 - 1998

N2 - A combined density functional and molecular mechanics approach (QM/MM) has been validated in a study of the substitution reactions: (i) (PH3)2Fe(CO)3 + 2ER3 mutually implies (ER3)2Fe(CO)3 + 2PH3 (ER3 = PMe3, PEt3, PMePh2, PPh3, PCyPh2, P(i)Pr3, PBz3, PCy3, AsEt3, AsPh3); and (ii) Cp'Ru(PH3)2Cl + 2ER3 mutually implies Cp'Ru(ER3)2Cl + 2PH3 (Cp' = C5H5, C5(CH3)5; ER3 = PMe3, PEt3 P(n)Bu3, PMe2Ph, PMePh2, PPh3, AsEt3, P(OMe)3, P(OPh)3, P(OCH2)3CEt). The steric influence of the R substituents on the substitution enthalpies correlates well with experimental data. The combined QM/MM approach is also able to afford molecular structures in good accord with experimental estimates.

AB - A combined density functional and molecular mechanics approach (QM/MM) has been validated in a study of the substitution reactions: (i) (PH3)2Fe(CO)3 + 2ER3 mutually implies (ER3)2Fe(CO)3 + 2PH3 (ER3 = PMe3, PEt3, PMePh2, PPh3, PCyPh2, P(i)Pr3, PBz3, PCy3, AsEt3, AsPh3); and (ii) Cp'Ru(PH3)2Cl + 2ER3 mutually implies Cp'Ru(ER3)2Cl + 2PH3 (Cp' = C5H5, C5(CH3)5; ER3 = PMe3, PEt3 P(n)Bu3, PMe2Ph, PMePh2, PPh3, AsEt3, P(OMe)3, P(OPh)3, P(OCH2)3CEt). The steric influence of the R substituents on the substitution enthalpies correlates well with experimental data. The combined QM/MM approach is also able to afford molecular structures in good accord with experimental estimates.

KW - Combined QM/MM

KW - Ligand substitutions

KW - Organometallic complexes

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DO - 10.1139/v98-169

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