Reversible Dihydrogen Activation and Catalytic H/D Exchange with Group 10 Heterometallic Complexes

01 September 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Reaction of a hexagonal planar palladium complex with a [PdMg3H3] core with H2 is reversible and leads to the formation of a new [PdMg2H4] tetrahydride species alongside an equivalent of a magnesium hydride co-product [MgH]. While the reversibility of this process prevented isolation and structural characterisation of [PdMg2H4], analogous [PtMg2H4] and [PdZn2H4] complexes could be isolated and characterised through independent syntheses. Computational analysis (DFT, AIM, NCIPlot) of the bonding in a series of heterometallic tetrahydride compounds (Ni-Pt; Mg and Zn) suggests that these complexes are best described as square planar with marginal metal–metal interactions; the strength of which increases as group 10 is descended and increases from Mg to Zn. DFT calculations support a mechanism for H2 activation involving a ligand-assisted oxidative addition to Pd. These findings were exploited to develop a catalytic protocol for H/D exchange into magnesium hydride and zinc hydride bonds.

Keywords

H2 activation
Heterometallic
Ligand-assisted Oxidative Addition
Hydrides
Metalloligands

Supplementary materials

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Supporting Information
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Experimental and computational procedures, along with associated data.
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Computational Coordinates
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XRD data
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