Activation of CO by hydrogenated magnesium(I) dimers: sterically controlled formation of ethenediolate and cyclopropanetriolate complexes

Ralte Lalrempuia; Christos E. Kefalidis; Simon James Bonyhady; Benedikt Schwarze; Laurent Maron; Andreas Stasch; Cameron Jones

doi:10.1021/jacs.5b06439

Activation of CO by hydrogenated magnesium(I) dimers: sterically controlled formation of ethenediolate and cyclopropanetriolate complexes

Ralte Lalrempuia, Christos E. Kefalidis, Simon James Bonyhady, Benedikt Schwarze, Laurent Maron^*, Andreas Stasch^*, Cameron Jones^*

^*Corresponding author for this work

School of Chemistry

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

Abstract

This study details the formal hydrogenation of two magnesium(I) dimers {(Nacnac)Mg}₂(Nacnac = [{(C₆H₃R₂-2,6)NCMe}₂CH]⁻; R = Prⁱ (^DipNacnac), Et (^DepNacnac)) using 1,3-cyclohexadiene. These reactions afford the magnesium(II) hydride complexes, {(Nacnac)Mg(μ-H)}₂. Their reactions with excess CO are sterically controlled and lead cleanly to different C–C coupled products, viz. the ethenediolate complex, (^DipNacnac)Mg{κ¹-O-[(^DipNacnac)Mg(κ²-O,O-O₂C₂H₂)]}, and the first cyclopropanetriolate complex of any metal, cis-{(^DepNacnac)Mg}₃{μ-C₃(H₃)O₃}. Computational studies imply the CO activation processes proceed via very similar mechanisms to those previously reported for related reactions involving f-block metal hydride compounds. This work highlights the potential magnesium compounds hold for use in the “Fischer–Tropsch-like” transformation of CO/H₂ mixtures to value added oxygenate products.

Original language	English
Pages (from-to)	8944 - 8947
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	28
Early online date	9 Jul 2015
DOIs	https://doi.org/10.1021/jacs.5b06439
Publication status	Published - 22 Jul 2015

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10.1021/jacs.5b06439

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@article{c7f34aaa09504d26b9b8eaeea45d0143,

title = "Activation of CO by hydrogenated magnesium(I) dimers: sterically controlled formation of ethenediolate and cyclopropanetriolate complexes",

abstract = "This study details the formal hydrogenation of two magnesium(I) dimers \{(Nacnac)Mg\}2 (Nacnac = [\{(C6H3R2-2,6)NCMe\}2CH]−; R = Pri (DipNacnac), Et (DepNacnac)) using 1,3-cyclohexadiene. These reactions afford the magnesium(II) hydride complexes, \{(Nacnac)Mg(μ-H)\}2. Their reactions with excess CO are sterically controlled and lead cleanly to different C–C coupled products, viz. the ethenediolate complex, (DipNacnac)Mg\{κ1-O-[(DipNacnac)Mg(κ2-O,O-O2C2H2)]\}, and the first cyclopropanetriolate complex of any metal, cis-\{(DepNacnac)Mg\}3\{μ-C3(H3)O3\}. Computational studies imply the CO activation processes proceed via very similar mechanisms to those previously reported for related reactions involving f-block metal hydride compounds. This work highlights the potential magnesium compounds hold for use in the “Fischer–Tropsch-like” transformation of CO/H2 mixtures to value added oxygenate products.",

author = "Ralte Lalrempuia and Kefalidis, \{Christos E.\} and Bonyhady, \{Simon James\} and Benedikt Schwarze and Laurent Maron and Andreas Stasch and Cameron Jones",

note = "Financial support from the Australian Research Council (C.J., A.S.), the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043 to C.J.), and the Alexander von Humboldt Foundation (grant of experienced researcher to L.M.), is acknowledged. Part of this research was undertaken on the MX1 beamline at the Australian Synchrotron, Victoria, Australia.",

year = "2015",

month = jul,

day = "22",

doi = "10.1021/jacs.5b06439",

language = "English",

volume = "137",

pages = "8944 -- 8947",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society (ACS)",

number = "28",

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Activation of CO by hydrogenated magnesium(I) dimers: sterically controlled formation of ethenediolate and cyclopropanetriolate complexes. / Lalrempuia, Ralte; Kefalidis, Christos E.; Bonyhady, Simon James et al.
In: Journal of the American Chemical Society, Vol. 137, No. 28, 22.07.2015, p. 8944 - 8947.

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

TY - JOUR

T1 - Activation of CO by hydrogenated magnesium(I) dimers

T2 - sterically controlled formation of ethenediolate and cyclopropanetriolate complexes

AU - Lalrempuia, Ralte

AU - Kefalidis, Christos E.

AU - Bonyhady, Simon James

AU - Schwarze, Benedikt

AU - Maron, Laurent

AU - Stasch, Andreas

AU - Jones, Cameron

N1 - Financial support from the Australian Research Council (C.J., A.S.), the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043 to C.J.), and the Alexander von Humboldt Foundation (grant of experienced researcher to L.M.), is acknowledged. Part of this research was undertaken on the MX1 beamline at the Australian Synchrotron, Victoria, Australia.

PY - 2015/7/22

Y1 - 2015/7/22

N2 - This study details the formal hydrogenation of two magnesium(I) dimers {(Nacnac)Mg}2 (Nacnac = [{(C6H3R2-2,6)NCMe}2CH]−; R = Pri (DipNacnac), Et (DepNacnac)) using 1,3-cyclohexadiene. These reactions afford the magnesium(II) hydride complexes, {(Nacnac)Mg(μ-H)}2. Their reactions with excess CO are sterically controlled and lead cleanly to different C–C coupled products, viz. the ethenediolate complex, (DipNacnac)Mg{κ1-O-[(DipNacnac)Mg(κ2-O,O-O2C2H2)]}, and the first cyclopropanetriolate complex of any metal, cis-{(DepNacnac)Mg}3{μ-C3(H3)O3}. Computational studies imply the CO activation processes proceed via very similar mechanisms to those previously reported for related reactions involving f-block metal hydride compounds. This work highlights the potential magnesium compounds hold for use in the “Fischer–Tropsch-like” transformation of CO/H2 mixtures to value added oxygenate products.

AB - This study details the formal hydrogenation of two magnesium(I) dimers {(Nacnac)Mg}2 (Nacnac = [{(C6H3R2-2,6)NCMe}2CH]−; R = Pri (DipNacnac), Et (DepNacnac)) using 1,3-cyclohexadiene. These reactions afford the magnesium(II) hydride complexes, {(Nacnac)Mg(μ-H)}2. Their reactions with excess CO are sterically controlled and lead cleanly to different C–C coupled products, viz. the ethenediolate complex, (DipNacnac)Mg{κ1-O-[(DipNacnac)Mg(κ2-O,O-O2C2H2)]}, and the first cyclopropanetriolate complex of any metal, cis-{(DepNacnac)Mg}3{μ-C3(H3)O3}. Computational studies imply the CO activation processes proceed via very similar mechanisms to those previously reported for related reactions involving f-block metal hydride compounds. This work highlights the potential magnesium compounds hold for use in the “Fischer–Tropsch-like” transformation of CO/H2 mixtures to value added oxygenate products.

UR - https://www.scopus.com/pages/publications/84937704143

U2 - 10.1021/jacs.5b06439

DO - 10.1021/jacs.5b06439

M3 - Article

SN - 0002-7863

VL - 137

SP - 8944

EP - 8947

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 28

ER -

Activation of CO by hydrogenated magnesium(I) dimers: sterically controlled formation of ethenediolate and cyclopropanetriolate complexes

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Activation of CO by hydrogenated magnesium(I) dimers: sterically controlled formation of ethenediolate and cyclopropanetriolate complexes

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