Zintl cluster supported low coordinate Rh(i) centers for catalytic H/D exchange between H2 and D2

Oliver P.E. Townrow; Simon B. Duckett; Andrew S. Weller; Jose M. Goicoechea

doi:10.1039/d2sc02552c

Zintl cluster supported low coordinate Rh(i) centers for catalytic H/D exchange between H₂ and D₂

Oliver P.E. Townrow, Simon B. Duckett, Andrew S. Weller^*, Jose M. Goicoechea

^*Corresponding author for this work

Chemistry

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

Abstract

Ligand exchange reactions of [Rh(COD){η⁴-Ge₉(Hyp)₃}] with L-type nucleophiles such as PMe₃, PPh₃, IMe₄ (IMe₄ = 1,3,4,5-tetramethylimidazol-2-ylidene) or [W(Cp)₂H₂] result in the displacement of the COD ligand to afford clusters with coordinatively unsaturated trigonal pyramidal rhodium(i) centers [Rh(L){η³-Ge₉(Hyp)₃}]. These species can be readily protonated allowing access to cationic rhodium-hydride complexes, e.g. [RhH(PPh₃){η³-Ge₉(Hyp)₃}]⁺. These clusters act as catalysts in H/D exchange between H₂ and D₂ and alkene isomerisation, thereby illustrating that metal-functionalized Zintl clusters are active in both H-H and C-H bond activation processes. The mechanism of H/D exchange was probed using parahydrogen induced polarization experiments.

Original language	English
Pages (from-to)	7626-7633
Number of pages	8
Journal	Chemical Science
Volume	13
DOIs	https://doi.org/10.1039/d2sc02552c
Publication status	Published - 9 Jun 2022

Bibliographical note

Funding Information:
We thank Shell Global Solutions International B.V., the University of Oxford and the EPSRC for financial support of this research (Industrial CASE studentship O. P. E. T.; EP/M024210 ASW). The University of Oxford is also acknowledged for access to Chemical Crystallography facilities.

Publisher Copyright:
© 2022 The Royal Society of Chemistry

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10.1039/d2sc02552cLicence: CC BY

Zintl cluster supported low coordinate Rh(I) centers for catalytic H/D exchange between H2 and D2
© 2022 The Author(s)
Final published version, 839 KBLicence: CC BY

Cite this

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title = "Zintl cluster supported low coordinate Rh(i) centers for catalytic H/D exchange between H2 and D2",

abstract = "Ligand exchange reactions of [Rh(COD){η4-Ge9(Hyp)3}] with L-type nucleophiles such as PMe3, PPh3, IMe4 (IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) or [W(Cp)2H2] result in the displacement of the COD ligand to afford clusters with coordinatively unsaturated trigonal pyramidal rhodium(i) centers [Rh(L){η3-Ge9(Hyp)3}]. These species can be readily protonated allowing access to cationic rhodium-hydride complexes, e.g. [RhH(PPh3){η3-Ge9(Hyp)3}]+. These clusters act as catalysts in H/D exchange between H2 and D2 and alkene isomerisation, thereby illustrating that metal-functionalized Zintl clusters are active in both H-H and C-H bond activation processes. The mechanism of H/D exchange was probed using parahydrogen induced polarization experiments.",

author = "Townrow, {Oliver P.E.} and Duckett, {Simon B.} and Weller, {Andrew S.} and Goicoechea, {Jose M.}",

note = "Funding Information: We thank Shell Global Solutions International B.V., the University of Oxford and the EPSRC for financial support of this research (Industrial CASE studentship O. P. E. T.; EP/M024210 ASW). The University of Oxford is also acknowledged for access to Chemical Crystallography facilities. Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry",

year = "2022",

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doi = "10.1039/d2sc02552c",

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AU - Townrow, Oliver P.E.

AU - Duckett, Simon B.

AU - Weller, Andrew S.

AU - Goicoechea, Jose M.

N1 - Funding Information: We thank Shell Global Solutions International B.V., the University of Oxford and the EPSRC for financial support of this research (Industrial CASE studentship O. P. E. T.; EP/M024210 ASW). The University of Oxford is also acknowledged for access to Chemical Crystallography facilities. Publisher Copyright: © 2022 The Royal Society of Chemistry

PY - 2022/6/9

Y1 - 2022/6/9

N2 - Ligand exchange reactions of [Rh(COD){η4-Ge9(Hyp)3}] with L-type nucleophiles such as PMe3, PPh3, IMe4 (IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) or [W(Cp)2H2] result in the displacement of the COD ligand to afford clusters with coordinatively unsaturated trigonal pyramidal rhodium(i) centers [Rh(L){η3-Ge9(Hyp)3}]. These species can be readily protonated allowing access to cationic rhodium-hydride complexes, e.g. [RhH(PPh3){η3-Ge9(Hyp)3}]+. These clusters act as catalysts in H/D exchange between H2 and D2 and alkene isomerisation, thereby illustrating that metal-functionalized Zintl clusters are active in both H-H and C-H bond activation processes. The mechanism of H/D exchange was probed using parahydrogen induced polarization experiments.

AB - Ligand exchange reactions of [Rh(COD){η4-Ge9(Hyp)3}] with L-type nucleophiles such as PMe3, PPh3, IMe4 (IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) or [W(Cp)2H2] result in the displacement of the COD ligand to afford clusters with coordinatively unsaturated trigonal pyramidal rhodium(i) centers [Rh(L){η3-Ge9(Hyp)3}]. These species can be readily protonated allowing access to cationic rhodium-hydride complexes, e.g. [RhH(PPh3){η3-Ge9(Hyp)3}]+. These clusters act as catalysts in H/D exchange between H2 and D2 and alkene isomerisation, thereby illustrating that metal-functionalized Zintl clusters are active in both H-H and C-H bond activation processes. The mechanism of H/D exchange was probed using parahydrogen induced polarization experiments.

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