Isomerism of [Ru(η3-allyl)Cl(CO)(PPh3) 2]

Peng Xue; Siwei Bi; Herman H.Y. Sung; Ian D. Williams; Zhenyang Lin; Guochen Jia

doi:10.1021/om049646g

Isomerism of [Ru(η³-allyl)Cl(CO)(PPh₃) ₂]

Peng Xue, Siwei Bi, Herman H.Y. Sung, Ian D. Williams, Zhenyang Lin^*, Guochen Jia

^*Corresponding author for this work

Department of Chemistry

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

70 Citations (Scopus)

Abstract

Treatment of [RuHCl(CO)(PPh₃)₃] with CH ₂=C=CMe₂ produced the new allyl complex [Ru(ζ³-CH₂CHCMe₂)Cl(CO)(PPh ₃)₂], which slowly isomerizes to [Ru(ζ³- CH₂CMeCHMe)Cl-(CO)(PPh₃)₂] in both solution and the solid state. While both endo and exo isomers can be observed by solution NMR for the allyl complex [Ru(ζ³-CH₂CHCMe ₂)Cl(CO)(PPh₃)₂], only the endo isomer was detected for other related analogous allyl complexes [Ru(ζ³- allyl)Cl-(CO)(PPh₃)₂] (e.g. allyl = CH₂CMeCHMe, CH₂CHCHPh). The isomeric behavior has been investigated by computational chemistry. The theoretical calculations show that the metal-ζ³-allyl interaction in an endo isomer of [Ru(ζ³-allyl)Cl(CO)(PR₃)₂] complexes is stronger than that in an exo isomer, because the structural arrangement provides an optimal situation to maximize the Ru(d)-to-CO(μ*) back-bonding interaction. However, substituents at the ζ³-allyl ligand also play an important role in determining the relative stability. It was found that an anti substituent (with respect to the central allylic substituent) at one of the terminal carbons destabilizes the endo isomer more significantly and therefore makes the endo and exo isomers comparable in terms of their relative stabilities. A syn substituent at one of the terminal carbons is, however, found to have a negligible effect on the relative stability. The endo-exo interconversion was found to proceed by intervention of ζ¹-allyl intermediates instead of a direct ζ³-allyl rotation.

Original language	English
Pages (from-to)	4735-4743
Number of pages	9
Journal	Organometallics
Volume	23
Issue number	20
DOIs	https://doi.org/10.1021/om049646g
Publication status	Published - 27 Sept 2004

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@article{bcf9f7a828904495aab42a96ba43f16f,

title = "Isomerism of [Ru(η3-allyl)Cl(CO)(PPh3) 2]",

abstract = "Treatment of [RuHCl(CO)(PPh3)3] with CH 2=C=CMe2 produced the new allyl complex [Ru(ζ3-CH2CHCMe2)Cl(CO)(PPh 3)2], which slowly isomerizes to [Ru(ζ3- CH2CMeCHMe)Cl-(CO)(PPh3)2] in both solution and the solid state. While both endo and exo isomers can be observed by solution NMR for the allyl complex [Ru(ζ3-CH2CHCMe 2)Cl(CO)(PPh3)2], only the endo isomer was detected for other related analogous allyl complexes [Ru(ζ3- allyl)Cl-(CO)(PPh3)2] (e.g. allyl = CH2CMeCHMe, CH2CHCHPh). The isomeric behavior has been investigated by computational chemistry. The theoretical calculations show that the metal-ζ3-allyl interaction in an endo isomer of [Ru(ζ3-allyl)Cl(CO)(PR3)2] complexes is stronger than that in an exo isomer, because the structural arrangement provides an optimal situation to maximize the Ru(d)-to-CO(μ*) back-bonding interaction. However, substituents at the ζ3-allyl ligand also play an important role in determining the relative stability. It was found that an anti substituent (with respect to the central allylic substituent) at one of the terminal carbons destabilizes the endo isomer more significantly and therefore makes the endo and exo isomers comparable in terms of their relative stabilities. A syn substituent at one of the terminal carbons is, however, found to have a negligible effect on the relative stability. The endo-exo interconversion was found to proceed by intervention of ζ1-allyl intermediates instead of a direct ζ3-allyl rotation.",

author = "Peng Xue and Siwei Bi and Sung, \{Herman H.Y.\} and Williams, \{Ian D.\} and Zhenyang Lin and Guochen Jia",

year = "2004",

month = sep,

day = "27",

doi = "10.1021/om049646g",

language = "English",

volume = "23",

pages = "4735--4743",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "20",

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TY - JOUR

T1 - Isomerism of [Ru(η3-allyl)Cl(CO)(PPh3) 2]

AU - Xue, Peng

AU - Bi, Siwei

AU - Sung, Herman H.Y.

AU - Williams, Ian D.

AU - Lin, Zhenyang

AU - Jia, Guochen

PY - 2004/9/27

Y1 - 2004/9/27

N2 - Treatment of [RuHCl(CO)(PPh3)3] with CH 2=C=CMe2 produced the new allyl complex [Ru(ζ3-CH2CHCMe2)Cl(CO)(PPh 3)2], which slowly isomerizes to [Ru(ζ3- CH2CMeCHMe)Cl-(CO)(PPh3)2] in both solution and the solid state. While both endo and exo isomers can be observed by solution NMR for the allyl complex [Ru(ζ3-CH2CHCMe 2)Cl(CO)(PPh3)2], only the endo isomer was detected for other related analogous allyl complexes [Ru(ζ3- allyl)Cl-(CO)(PPh3)2] (e.g. allyl = CH2CMeCHMe, CH2CHCHPh). The isomeric behavior has been investigated by computational chemistry. The theoretical calculations show that the metal-ζ3-allyl interaction in an endo isomer of [Ru(ζ3-allyl)Cl(CO)(PR3)2] complexes is stronger than that in an exo isomer, because the structural arrangement provides an optimal situation to maximize the Ru(d)-to-CO(μ*) back-bonding interaction. However, substituents at the ζ3-allyl ligand also play an important role in determining the relative stability. It was found that an anti substituent (with respect to the central allylic substituent) at one of the terminal carbons destabilizes the endo isomer more significantly and therefore makes the endo and exo isomers comparable in terms of their relative stabilities. A syn substituent at one of the terminal carbons is, however, found to have a negligible effect on the relative stability. The endo-exo interconversion was found to proceed by intervention of ζ1-allyl intermediates instead of a direct ζ3-allyl rotation.

AB - Treatment of [RuHCl(CO)(PPh3)3] with CH 2=C=CMe2 produced the new allyl complex [Ru(ζ3-CH2CHCMe2)Cl(CO)(PPh 3)2], which slowly isomerizes to [Ru(ζ3- CH2CMeCHMe)Cl-(CO)(PPh3)2] in both solution and the solid state. While both endo and exo isomers can be observed by solution NMR for the allyl complex [Ru(ζ3-CH2CHCMe 2)Cl(CO)(PPh3)2], only the endo isomer was detected for other related analogous allyl complexes [Ru(ζ3- allyl)Cl-(CO)(PPh3)2] (e.g. allyl = CH2CMeCHMe, CH2CHCHPh). The isomeric behavior has been investigated by computational chemistry. The theoretical calculations show that the metal-ζ3-allyl interaction in an endo isomer of [Ru(ζ3-allyl)Cl(CO)(PR3)2] complexes is stronger than that in an exo isomer, because the structural arrangement provides an optimal situation to maximize the Ru(d)-to-CO(μ*) back-bonding interaction. However, substituents at the ζ3-allyl ligand also play an important role in determining the relative stability. It was found that an anti substituent (with respect to the central allylic substituent) at one of the terminal carbons destabilizes the endo isomer more significantly and therefore makes the endo and exo isomers comparable in terms of their relative stabilities. A syn substituent at one of the terminal carbons is, however, found to have a negligible effect on the relative stability. The endo-exo interconversion was found to proceed by intervention of ζ1-allyl intermediates instead of a direct ζ3-allyl rotation.

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:000223991700029

UR - https://openalex.org/W2039847301

UR - https://www.scopus.com/pages/publications/4944230200

U2 - 10.1021/om049646g

DO - 10.1021/om049646g

M3 - Journal Article

SN - 0276-7333

VL - 23

SP - 4735

EP - 4743

JO - Organometallics

JF - Organometallics

IS - 20

ER -

Isomerism of [Ru(η³-allyl)Cl(CO)(PPh₃) ₂]

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