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Inorganic Chemistry

Transition-metal complex takes on an unexpected hexagonal planar structure

Stable palladium complex has 3 hydrides and 3 magnesium ligands

by Leigh Krietsch Boerner
October 12, 2019 | APPEARED IN VOLUME 97, ISSUE 40

 

09740-scicon6-structure.jpg
Credit: Imperial College London
A palladium complex takes on a rarely seen hexagonal planar structure.

The geometries of transition-metal complexes are a small clique. The atoms and ligands in such complexes generally take on only a few structures, such as octahedral, trigonal bipyramidal, and square planar shapes. Scientists proposed a hexagonal planar geometry more than 100 years ago, but it has never been captured in crystal form until now. Mark R. Crimmin and coworkers at Imperial College London nabbed the structure with a complex consisting of a palladium atom surrounded by three hydride and three magnesium-diisopropylphenyl ligands (Nature 2019, DOI: 10.1038/s41586-019-1616-2). Scientists know that hexagonal planar compounds can form in condensed metal phases and in the pores of coordination polymers, but a transition-metal complex with this geometry was a surprise, Crimmin says. “The magnesium ligands accept electron density from the palladium,” and, with this geometry, they interact optimally with palladium's filled d orbitals to stabilize the compound, he adds. “Not only does this species have the potential for interesting reactivity,” says Michael Whittlesey of the University of Bath, but it suggests that combining transition metals with other nonconventional main-group metals may give rise to compounds with unexpected properties.

Credit: Imperial College London
The crystal structure of the palladium hexagonal planar complex.

CORRECTION

This story was updated on Oct. 15, 2019, to correct the statement that the hydrides overlap well with filled palladium d orbitals. The magnesium ligands are what interact with palladium's d orbitals.

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