Isomerization of the osmium-tellurium cluster Os3(μ-TeR)2(CO)10: A kinetic and computational study

E. K.S. Shim; W. K. Leong; Y. Z. Li; M. G. Richmond

doi:10.1039/c6dt00588h

Isomerization of the osmium-tellurium cluster Os₃(μ-TeR)₂(CO)₁₀: A kinetic and computational study

E. K.S. Shim, W. K. Leong^*, Y. Z. Li, M. G. Richmond

^*Corresponding author for this work

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

1 Citation (Scopus)

Abstract

The kinetics for the isomerization of the 50e cluster Os₃(μ-TeTol-p)₂(CO)₁₀ (3), where the tellurides bridge two different Os-Os edges, to one in which the tellurides bridge the same open Os⋯Os edge (4) have been measured experimentally by ¹H NMR spectroscopy. The determined activation parameters are ΔH^‡ = 77 ± 9 kJ mol^-1 and ΔS^‡ = -12 ± 28 J mol^-1 K. The conversion of 3 to 4 has been computationally investigated by electronic structure calculations using the model compound Os₃(μ-TeMe)₂(CO)₁₀. The computed isomerization pathway is consistent with the kinetic data and the thermodynamic preference for the product stereoisomer that possesses a slipped, eclipsed conformation for the two p-tolyl groups.

Original language	English
Pages (from-to)	7158-7162
Number of pages	5
Journal	Dalton Transactions
Volume	45
Issue number	16
DOIs	https://doi.org/10.1039/c6dt00588h
Publication status	Published - Apr 28 2016
Externally published	Yes

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry 2016.

ASJC Scopus Subject Areas

Inorganic Chemistry

Access to Document

10.1039/c6dt00588h

Cite this

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title = "Isomerization of the osmium-tellurium cluster Os3(μ-TeR)2(CO)10: A kinetic and computational study",

abstract = "The kinetics for the isomerization of the 50e cluster Os3(μ-TeTol-p)2(CO)10 (3), where the tellurides bridge two different Os-Os edges, to one in which the tellurides bridge the same open Os⋯Os edge (4) have been measured experimentally by 1H NMR spectroscopy. The determined activation parameters are ΔH‡ = 77 ± 9 kJ mol-1 and ΔS‡ = -12 ± 28 J mol-1 K. The conversion of 3 to 4 has been computationally investigated by electronic structure calculations using the model compound Os3(μ-TeMe)2(CO)10. The computed isomerization pathway is consistent with the kinetic data and the thermodynamic preference for the product stereoisomer that possesses a slipped, eclipsed conformation for the two p-tolyl groups.",

author = "Shim, {E. K.S.} and Leong, {W. K.} and Li, {Y. Z.} and Richmond, {M. G.}",

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T1 - Isomerization of the osmium-tellurium cluster Os3(μ-TeR)2(CO)10

T2 - A kinetic and computational study

AU - Shim, E. K.S.

AU - Leong, W. K.

AU - Li, Y. Z.

AU - Richmond, M. G.

PY - 2016/4/28

Y1 - 2016/4/28

N2 - The kinetics for the isomerization of the 50e cluster Os3(μ-TeTol-p)2(CO)10 (3), where the tellurides bridge two different Os-Os edges, to one in which the tellurides bridge the same open Os⋯Os edge (4) have been measured experimentally by 1H NMR spectroscopy. The determined activation parameters are ΔH‡ = 77 ± 9 kJ mol-1 and ΔS‡ = -12 ± 28 J mol-1 K. The conversion of 3 to 4 has been computationally investigated by electronic structure calculations using the model compound Os3(μ-TeMe)2(CO)10. The computed isomerization pathway is consistent with the kinetic data and the thermodynamic preference for the product stereoisomer that possesses a slipped, eclipsed conformation for the two p-tolyl groups.

AB - The kinetics for the isomerization of the 50e cluster Os3(μ-TeTol-p)2(CO)10 (3), where the tellurides bridge two different Os-Os edges, to one in which the tellurides bridge the same open Os⋯Os edge (4) have been measured experimentally by 1H NMR spectroscopy. The determined activation parameters are ΔH‡ = 77 ± 9 kJ mol-1 and ΔS‡ = -12 ± 28 J mol-1 K. The conversion of 3 to 4 has been computationally investigated by electronic structure calculations using the model compound Os3(μ-TeMe)2(CO)10. The computed isomerization pathway is consistent with the kinetic data and the thermodynamic preference for the product stereoisomer that possesses a slipped, eclipsed conformation for the two p-tolyl groups.

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