Imperial College London
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Professor Mark R. Crimmin

Faculty of Natural Sciences, Department of Chemistry

Professor of Organometallic Chemistry
 
 
 
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Contact

 

+44 (0)20 7594 2846m.crimmin Website

 
 
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Location

 

501NMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Hooper:2019:10.1039/c9sc02750e,
author = {Hooper, TN and Lau, S and Chen, W and Brown, RK and Garçon, M and Luong, K and Barrow, NS and Tatton, AS and Sackman, GA and Richardson, C and White, AJP and Cooper, RI and Edwards, AJ and Casely, IJ and Crimmin, MR},
doi = {10.1039/c9sc02750e},
journal = {Chemical Science},
pages = {8083--8093},
title = {The partial dehydrogenation of aluminium dihydrides},
url = {http://dx.doi.org/10.1039/c9sc02750e},
volume = {10},
year = {2019}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - The reactions of a series of β-diketiminate stabilised aluminium dihydrides with ruthenium bis(phosphine), palladium bis(phosphine) and palladium cyclopentadienyl complexes is reported. In the case of ruthenium, alane coordination occurs with no evidence for hydrogen loss resulting in the formation of ruthenium complexes with a pseudo–octahedral geometry and cis-relation of phosphine ligands. These new ruthenium complexes have been characterised by multinuclear and variable temperature NMR spectroscopy, IR spectroscopy and single crystal X-ray diffraction. In the case of palladium, a series of structural snapshots of alane dehydrogenation have been isolated and crystallographically characterised. Variation of the palladium precursor and ligand on aluminium allows kinetic control over reactivity and isolation of intermetallic complexes that contain new Pd–Al and Pd–Pd interactions. These complexes differ by the ratio of H:Al (2:1, 1.5:1 and 1:1) with lower hydride content species forming with dihydrogen loss. A combination of X-ray and neutron diffraction studies have been used to interrogate the structures and provide confidence in the assignment of the number and position of hydride ligands. 27Al MAS NMR spectroscopy and calculations (DFT, QTAIM) have been used to gain an understanding of the dehydrogenation processes. The latter provide evidence for dehydrogenation being accompanied by metal–metal bond formation and an increased negative charge on Al due to the covalency of the new metal–metal bonds. To the best of our knowledge, we present the first structural information for intermediate species in alane dehydrogenation including a rare neutron diffraction study of a palladium–aluminium hydride complex. Furthermore, as part of these studies we have obtained the first SS 27Al NMR data on an aluminium(I) complex. Our findings are relevant to hydrogen storage, materials chemistry and catalysis.
AU  - Hooper,TN
AU  - Lau,S
AU  - Chen,W
AU  - Brown,RK
AU  - Garçon,M
AU  - Luong,K
AU  - Barrow,NS
AU  - Tatton,AS
AU  - Sackman,GA
AU  - Richardson,C
AU  - White,AJP
AU  - Cooper,RI
AU  - Edwards,AJ
AU  - Casely,IJ
AU  - Crimmin,MR
DO  - 10.1039/c9sc02750e
EP  - 8093
PY  - 2019///
SN  - 2041-6520
SP  - 8083
TI  - The partial dehydrogenation of aluminium dihydrides
T2  - Chemical Science
UR  - http://dx.doi.org/10.1039/c9sc02750e
UR  - http://hdl.handle.net/10044/1/73353
VL  - 10
ER  -
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