Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex

Laurence R. Doyle; Martin R. Galpin; Samantha K. Furfari; Bengt E. Tegner; Antonio J. Martínez-Martínez; Adrian C. Whitwood; Scott A. Hicks; Guy C. Lloyd-Jones; Stuart A. MacGregor; Andrew S. Weller

doi:10.1021/acs.organomet.1c00639

Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex

Laurence R. Doyle^*, Martin R. Galpin, Samantha K. Furfari, Bengt E. Tegner, Antonio J. Martínez-Martínez, Adrian C. Whitwood, Scott A. Hicks, Guy C. Lloyd-Jones, Stuart A. MacGregor, Andrew S. Weller

^*Corresponding author for this work

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Abstract

The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy₂P(CH₂)₃PCy₂)(COD)][BAr^F₄] (COD = cyclooctadiene) with H₂ or D₂ was followed in situ by solid-state ³¹P{¹H} NMR spectroscopy (SSNMR) and ex situ by solution quenching and GC-MS. This was quantified using a two-step Johnson–Mehl–Avrami–Kologoromov (JMAK) model that revealed an inverse isotope effect for the second addition of H₂, that forms a σ-alkane complex [Rh(Cy₂P(CH₂)₃PCy₂)(COA)][BAr^F₄]. Using D₂, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an η²,η²-binding mode to the Rh(I) center, as supported by periodic density functional theory (DFT) calculations. Extensive H/D exchange occurs during the addition of D₂, as promoted by the solid-state microenvironment.

Original language	English
Pages (from-to)	284–292
Number of pages	9
Journal	Organometallics
Volume	41
Issue number	3
Early online date	27 Jan 2022
DOIs	https://doi.org/10.1021/acs.organomet.1c00639
Publication status	Published - 14 Feb 2022

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Doyle, L. R., Galpin, M. R., Furfari, S. K., Tegner, B. E., Martínez-Martínez, A. J., Whitwood, A. C., Hicks, S. A., Lloyd-Jones, G. C., MacGregor, S. A., & Weller, A. S. (2022). Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex. Organometallics, 41(3), 284–292. https://doi.org/10.1021/acs.organomet.1c00639

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title = "Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex",

abstract = "The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF4] (COD = cyclooctadiene) with H2 or D2 was followed in situ by solid-state 31P{1H} NMR spectroscopy (SSNMR) and ex situ by solution quenching and GC-MS. This was quantified using a two-step Johnson–Mehl–Avrami–Kologoromov (JMAK) model that revealed an inverse isotope effect for the second addition of H2, that forms a σ-alkane complex [Rh(Cy2P(CH2)3PCy2)(COA)][BArF4]. Using D2, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an η2,η2-binding mode to the Rh(I) center, as supported by periodic density functional theory (DFT) calculations. Extensive H/D exchange occurs during the addition of D2, as promoted by the solid-state microenvironment.",

author = "Doyle, {Laurence R.} and Galpin, {Martin R.} and Furfari, {Samantha K.} and Tegner, {Bengt E.} and Mart{\'i}nez-Mart{\'i}nez, {Antonio J.} and Whitwood, {Adrian C.} and Hicks, {Scott A.} and Lloyd-Jones, {Guy C.} and MacGregor, {Stuart A.} and Weller, {Andrew S.}",

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doi = "10.1021/acs.organomet.1c00639",

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Doyle, LR, Galpin, MR, Furfari, SK, Tegner, BE, Martínez-Martínez, AJ, Whitwood, AC, Hicks, SA, Lloyd-Jones, GC, MacGregor, SA & Weller, AS 2022, 'Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex', Organometallics, vol. 41, no. 3, pp. 284–292. https://doi.org/10.1021/acs.organomet.1c00639

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T1 - Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex

AU - Doyle, Laurence R.

AU - Galpin, Martin R.

AU - Furfari, Samantha K.

AU - Tegner, Bengt E.

AU - Martínez-Martínez, Antonio J.

AU - Whitwood, Adrian C.

AU - Hicks, Scott A.

AU - Lloyd-Jones, Guy C.

AU - MacGregor, Stuart A.

AU - Weller, Andrew S.

PY - 2022/2/14

Y1 - 2022/2/14

N2 - The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF4] (COD = cyclooctadiene) with H2 or D2 was followed in situ by solid-state 31P{1H} NMR spectroscopy (SSNMR) and ex situ by solution quenching and GC-MS. This was quantified using a two-step Johnson–Mehl–Avrami–Kologoromov (JMAK) model that revealed an inverse isotope effect for the second addition of H2, that forms a σ-alkane complex [Rh(Cy2P(CH2)3PCy2)(COA)][BArF4]. Using D2, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an η2,η2-binding mode to the Rh(I) center, as supported by periodic density functional theory (DFT) calculations. Extensive H/D exchange occurs during the addition of D2, as promoted by the solid-state microenvironment.

AB - The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF4] (COD = cyclooctadiene) with H2 or D2 was followed in situ by solid-state 31P{1H} NMR spectroscopy (SSNMR) and ex situ by solution quenching and GC-MS. This was quantified using a two-step Johnson–Mehl–Avrami–Kologoromov (JMAK) model that revealed an inverse isotope effect for the second addition of H2, that forms a σ-alkane complex [Rh(Cy2P(CH2)3PCy2)(COA)][BArF4]. Using D2, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an η2,η2-binding mode to the Rh(I) center, as supported by periodic density functional theory (DFT) calculations. Extensive H/D exchange occurs during the addition of D2, as promoted by the solid-state microenvironment.

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Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex

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