Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters

Maximilian Muhr; Hao Liang; Lars Allmendinger; Raphael Bühler; Fabrizio E. Napoli; Dardan Ukaj; Mirza Cokoja; Christian Jandl; Samia Kahlal; Jean Yves Saillard; Christian Gemel; Roland A. Fischer

doi:10.1002/anie.202308790

Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters

Maximilian Muhr, Hao Liang, Lars Allmendinger, Raphael Bühler, Fabrizio E. Napoli, Dardan Ukaj, Mirza Cokoja, Christian Jandl, Samia Kahlal, Jean Yves Saillard, Christian Gemel, Roland A. Fischer

Chair of Inorganic and Organometallic Chemistry

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

6 Scopus citations

Abstract

The bimetallic, decanuclear Ni₃Ga₇-cluster of the formula [Ni₃(GaTMP)₃(μ²-GaTMP)₃(μ³-GaTMP)] (1, TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2. Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- (2_Di), tetra- (2_Tetra) and hexahydride species (2_Hexa). The structures of 2_Di and 2_Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis.

Original language	English
Article number	e202308790
Journal	Angewandte Chemie International Edition in English
Volume	62
Issue number	36
DOIs	https://doi.org/10.1002/anie.202308790
State	Published - 4 Sep 2023

Keywords

(Poly-) Hydrides
Density Functional Calculations
Metal Cluster
ROESY
Semihydrogenation Catalysis

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10.1002/anie.202308790

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title = "Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters",

abstract = "The bimetallic, decanuclear Ni3Ga7-cluster of the formula [Ni3(GaTMP)3(μ2-GaTMP)3(μ3-GaTMP)] (1, TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2. Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- (2Di), tetra- (2Tetra) and hexahydride species (2Hexa). The structures of 2Di and 2Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis.",

keywords = "(Poly-) Hydrides, Density Functional Calculations, Metal Cluster, ROESY, Semihydrogenation Catalysis",

author = "Maximilian Muhr and Hao Liang and Lars Allmendinger and Raphael B{\"u}hler and Napoli, {Fabrizio E.} and Dardan Ukaj and Mirza Cokoja and Christian Jandl and Samia Kahlal and Saillard, {Jean Yves} and Christian Gemel and Fischer, {Roland A.}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2023",

month = sep,

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doi = "10.1002/anie.202308790",

language = "English",

volume = "62",

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TY - JOUR

T1 - Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters

AU - Muhr, Maximilian

AU - Liang, Hao

AU - Allmendinger, Lars

AU - Bühler, Raphael

AU - Napoli, Fabrizio E.

AU - Ukaj, Dardan

AU - Cokoja, Mirza

AU - Jandl, Christian

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Gemel, Christian

AU - Fischer, Roland A.

PY - 2023/9/4

Y1 - 2023/9/4

N2 - The bimetallic, decanuclear Ni3Ga7-cluster of the formula [Ni3(GaTMP)3(μ2-GaTMP)3(μ3-GaTMP)] (1, TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2. Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- (2Di), tetra- (2Tetra) and hexahydride species (2Hexa). The structures of 2Di and 2Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis.

AB - The bimetallic, decanuclear Ni3Ga7-cluster of the formula [Ni3(GaTMP)3(μ2-GaTMP)3(μ3-GaTMP)] (1, TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2. Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- (2Di), tetra- (2Tetra) and hexahydride species (2Hexa). The structures of 2Di and 2Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis.

KW - (Poly-) Hydrides

KW - Density Functional Calculations

KW - Metal Cluster

KW - ROESY

KW - Semihydrogenation Catalysis

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ER -

Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters

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