MicroED characterization of a robust cationic σ-alkane complex stabilized by the [B(3,5-(SF5)2C6H3)4]− anion, via on-grid solid/gas single-crystal to single-crystal reactivity

Abstract

Microcrystalline (∼1 μm) [Rh(Cy₂PCH₂CH₂PCy₂)(norbornadiene)][S-BAr^F₄], [S-BAr^F₄] = [B(3,5-(SF₅)₂C₆H₃)₄]⁻, reacts with H₂ in a single-crystal to single-crystal transformation to form the σ-alkane complex [Rh(Cy₂PCH₂CH₂PCy₂)(norbornane)][S-BAr^F₄], for which the structure was determined by microcrystal Electron Diffraction (microED), to 0.95 Å resolution, via an on-grid hydrogenation, and a complementary single-crystal X-ray diffraction study on larger, but challenging to isolate, crystals. Comparison with the [BAr^F₄]⁻ analogue [Ar^F = 3,5-(CF₃)₂(C₆H₃)] shows that the [S-BAr^F₄]⁻ anion makes the σ-alkane complex robust towards decomposition both thermally and when suspended in pentane. Subsequent reactivity with dissolved ethene in a pentane slurry, forms [Rh(Cy₂PCH₂CH₂PCy₂)(ethene)₂][S-BAr^F₄], and the catalytic dimerisation/isomerisation of ethene to 2-butenes. The increased stability of [S-BAr^F₄]⁻ salts is identified as being due to increased non-covalent interactions in the lattice, resulting in a solid-state molecular organometallic material with desirable stability characteristics.