Structural Snapshots of an Al–Cu Bond-Mediated Transformation of Terminal Acetylenes

Han-Ying Dennis Liu; Samuel E. Neale; Michael S. Hill; Mary F. Mahon; Claire L. McMullin

doi:10.1039/d3sc00240c

Structural Snapshots of an Al–Cu Bond-Mediated Transformation of Terminal Acetylenes

Han-Ying Dennis Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin

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Abstract

The copper(i) alumanyl derivative, [{SiN ^Dipp}Al-Cu(NHC ^iPr)] (SiN ^Dipp = {CH ₂SiMe ₂NDipp} ₂; Dipp = 2,6-di-isopropylphenyl; NHC ^iPr = N,N′-di-isopropyl-4,5-dimethyl-2-ylidene), reacts in a stepwise fashion with up to three equivalents of various terminal alkynes. This reactivity results in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate and bis(alkynyl)aluminate derivatives, examples of which have been fully characterised. The process of alkene liberation resulting from the latter reaction step constitutes a unique case of alkyne transfer semi-hydrogenation in which the C-H acidic alkyne itself acts as a source of proton, with the Cu-Al bond providing the requisite electrons to effect reduction. This reaction sequence is validated by DFT calculations, which rationalise the variable stability of the initially formed heterobimetallic hydrides.

Original language	English
Pages (from-to)	2866 - 2876
Number of pages	11
Journal	Chemical Science
Volume	14
Issue number	11
Early online date	15 Feb 2023
DOIs	https://doi.org/10.1039/d3sc00240c
Publication status	Published - 15 Feb 2023

Bibliographical note

We acknowledge financial support from the EPSRC (research grant EP/R020752/1). This research made use of the Anatra High Throughput Computing (HTC) Cluster at the University of Bath. The authors gratefully acknowledge the University of Bath’s Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work.

The Supporting Information, including experimental details, NMR spectra and details of the computational and single crystal X-ray diffraction analysis, is available free of charge at XXXXX. CCDC codes 2234315-2234325 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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10.1039/d3sc00240cLicence: CC BY

Cite this

@article{c0e21694043f49bf8b7d7f6e9e40b48f,

title = "Structural Snapshots of an Al–Cu Bond-Mediated Transformation of Terminal Acetylenes",

abstract = "The copper(i) alumanyl derivative, [{SiN Dipp}Al-Cu(NHC iPr)] (SiN Dipp = {CH 2SiMe 2NDipp} 2; Dipp = 2,6-di-isopropylphenyl; NHC iPr = N,N′-di-isopropyl-4,5-dimethyl-2-ylidene), reacts in a stepwise fashion with up to three equivalents of various terminal alkynes. This reactivity results in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate and bis(alkynyl)aluminate derivatives, examples of which have been fully characterised. The process of alkene liberation resulting from the latter reaction step constitutes a unique case of alkyne transfer semi-hydrogenation in which the C-H acidic alkyne itself acts as a source of proton, with the Cu-Al bond providing the requisite electrons to effect reduction. This reaction sequence is validated by DFT calculations, which rationalise the variable stability of the initially formed heterobimetallic hydrides.",

author = "Liu, {Han-Ying Dennis} and Neale, {Samuel E.} and Hill, {Michael S.} and Mahon, {Mary F.} and McMullin, {Claire L.}",

note = "We acknowledge financial support from the EPSRC (research grant EP/R020752/1). This research made use of the Anatra High Throughput Computing (HTC) Cluster at the University of Bath. The authors gratefully acknowledge the University of Bath{\textquoteright}s Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work. The Supporting Information, including experimental details, NMR spectra and details of the computational and single crystal X-ray diffraction analysis, is available free of charge at XXXXX. CCDC codes 2234315-2234325 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.",

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T1 - Structural Snapshots of an Al–Cu Bond-Mediated Transformation of Terminal Acetylenes

AU - Liu, Han-Ying Dennis

AU - Neale, Samuel E.

AU - Hill, Michael S.

AU - Mahon, Mary F.

AU - McMullin, Claire L.

N1 - We acknowledge financial support from the EPSRC (research grant EP/R020752/1). This research made use of the Anatra High Throughput Computing (HTC) Cluster at the University of Bath. The authors gratefully acknowledge the University of Bath’s Research Computing Group (doi.org/10.15125/b6cd-s854) for their support in this work. The Supporting Information, including experimental details, NMR spectra and details of the computational and single crystal X-ray diffraction analysis, is available free of charge at XXXXX. CCDC codes 2234315-2234325 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

PY - 2023/2/15

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N2 - The copper(i) alumanyl derivative, [{SiN Dipp}Al-Cu(NHC iPr)] (SiN Dipp = {CH 2SiMe 2NDipp} 2; Dipp = 2,6-di-isopropylphenyl; NHC iPr = N,N′-di-isopropyl-4,5-dimethyl-2-ylidene), reacts in a stepwise fashion with up to three equivalents of various terminal alkynes. This reactivity results in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate and bis(alkynyl)aluminate derivatives, examples of which have been fully characterised. The process of alkene liberation resulting from the latter reaction step constitutes a unique case of alkyne transfer semi-hydrogenation in which the C-H acidic alkyne itself acts as a source of proton, with the Cu-Al bond providing the requisite electrons to effect reduction. This reaction sequence is validated by DFT calculations, which rationalise the variable stability of the initially formed heterobimetallic hydrides.

AB - The copper(i) alumanyl derivative, [{SiN Dipp}Al-Cu(NHC iPr)] (SiN Dipp = {CH 2SiMe 2NDipp} 2; Dipp = 2,6-di-isopropylphenyl; NHC iPr = N,N′-di-isopropyl-4,5-dimethyl-2-ylidene), reacts in a stepwise fashion with up to three equivalents of various terminal alkynes. This reactivity results in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate and bis(alkynyl)aluminate derivatives, examples of which have been fully characterised. The process of alkene liberation resulting from the latter reaction step constitutes a unique case of alkyne transfer semi-hydrogenation in which the C-H acidic alkyne itself acts as a source of proton, with the Cu-Al bond providing the requisite electrons to effect reduction. This reaction sequence is validated by DFT calculations, which rationalise the variable stability of the initially formed heterobimetallic hydrides.

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U2 - 10.1039/d3sc00240c

DO - 10.1039/d3sc00240c

M3 - Article

SN - 2041-6520

VL - 14

SP - 2866

EP - 2876

JO - Chemical Science

JF - Chemical Science

IS - 11

ER -

Structural Snapshots of an Al–Cu Bond-Mediated Transformation of Terminal Acetylenes

Abstract

Bibliographical note

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Nucleophilic alkaline earth boryls: from conception and theory to application

High Performance Computing (HPC) Facility

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Structural Snapshots of an Al–Cu Bond-Mediated Transformation of Terminal Acetylenes

Abstract

Bibliographical note

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Nucleophilic alkaline earth boryls: from conception and theory to application

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High Performance Computing (HPC) Facility

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