Controlling Structure and Reactivity in Cationic Solid-State Molecular Organometallic Systems Using Anion Templating

Alasdair I. McKay, Antonio J. Martínez-Martínez, Hannah J. Griffiths, Nicholas H. Rees, Jordan B. Waters, Andrew S. Weller*, Tobias Krämer, Stuart A. MacGregor

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)


The role that the supporting anion has on the stability, structure, and catalytic performance, in solid-state molecular organometallic systems (SMOM) based upon [Rh(Cy2PCH2CH2PCy2)(η2η2-NBD)][BArX 4], [1-NBD][BArX 4], is reported (X = Cl, F, H; NBD = norbornadiene). The tetra-aryl borate anion is systematically varied at the 3,5-position, ArX= 3,5-X2C6H3, and the stability and structure in the solid-state compared with the previously reported [1-NBD][BArCF3 4] complex. Single-crystal X-ray crystallography shows that the three complexes have different packing motifs, in which the cation sits on the shared face of two parallelepipeds for [1-NBD][BArCl 4], is surrounded by eight anions in a gyrobifastigium arrangement for [1-NBD][BArF 4], or the six anions show an octahedral cage arrangement in [1-NBD][BArH 4], similar to that of [1-NBD][BArCF3 4]. C-X···X-C contacts, commonly encountered in crystal-engineering, are suggested to be important in determining structure. Addition of H2 in a solid/gas reaction affords the resulting σ-alkane complexes, [Rh(Cy2PCH2CH2PCy2)(η2η2-NBA)][BArX 4] [1-NBA][BArX 4] (NBA = norbornane), which can then proceed to lose the alkane and form the zwitterionic, anion-coordinated, complexes. The relative rates at which hydrogenation and then decomposition of σ-alkane complexes proceed are shown to be anion dependent. [BArCF3 4]- promotes fast hydrogenation and an indefinitely stable σ-alkane complex. With [BArH 4]- hydrogenation is slow and the σ-alkane complex so unstable it is not observed. [BArCl 4]- and [BArF 4]- promote intermediate reactivity profiles, and for [BArCl 4]-, a single-crystal to single-crystal hydrogenation results in [1-NBA][BArCl 4]. The molecular structure derived from X-ray diffraction reveals a σ-alkane complex in which the NBA fragment is bound through two exo Rh···H-C interactions-different from the endo selective binding observed with [1-NBA][BArCF3 4]. Periodic DFT calculations demonstrate that this selectivity is driven by the microenvironment dictated by the surrounding anions. [1-NBA][BArX 4] are catalysts for gas/solid 1-butene isomerization (298 K, 1 atm), and their activity can be directly correlated to the stability of the σ-alkane complex compared to the anion-coordinated decomposition products.

Original languageEnglish
Pages (from-to)3524-3532
Number of pages9
Issue number20
Publication statusPublished - 22 Oct 2018


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