Doyle Laurence R, Thompson Emily A, Burnage Arron L, Whitwood Adrian C, Jenkins Huw T, Macgregor Stuart A, Weller Andrew S
Department of Chemistry, University of York, Heslington, York YO10 5DD, UK.
Institute of Chemical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UK.
Dalton Trans. 2022 Mar 1;51(9):3661-3665. doi: 10.1039/d2dt00335j.
Microcrystalline (∼1 μm) [Rh(CyPCHCHPCy)(norbornadiene)][S-BAr], [S-BAr] = [B(3,5-(SF)CH)], reacts with H in a single-crystal to single-crystal transformation to form the σ-alkane complex [Rh(CyPCHCHPCy)(norbornane)][S-BAr], for which the structure was determined by microcrystal Electron Diffraction (microED), to 0.95 Å resolution, an on-grid hydrogenation, and a complementary single-crystal X-ray diffraction study on larger, but challenging to isolate, crystals. Comparison with the [BAr] analogue [Ar = 3,5-(CF)(CH)] shows that the [S-BAr] 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(CyPCHCHPCy)(ethene)][S-BAr], and the catalytic dimerisation/isomerisation of ethene to 2-butenes. The increased stability of [S-BAr] 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.
微晶（约1μm）的[Rh(CyPCHCHPCy)(降冰片二烯)][S-BAr]，[S-BAr] = [B(3,5-(SF)CH)]，与氢气发生单晶到单晶的转变反应，形成σ-烷烃配合物[Rh(CyPCHCHPCy)(降冰片烷)][S-BAr]，其结构通过微晶电子衍射（microED）确定，分辨率达到0.95 Å，这是一种网格上的氢化反应，并且对较大但难以分离的晶体进行了补充单晶X射线衍射研究。与[BAr]类似物[Ar = 3,5-(CF)(CH)]的比较表明，[S-BAr]阴离子使σ-烷烃配合物在热稳定性以及悬浮于戊烷中时都对分解具有很强的抗性。随后，在戊烷浆液中与溶解的乙烯发生反应，形成[Rh(CyPCHCHPCy)(乙烯)][S-BAr]，以及乙烯催化二聚/异构化为2-丁烯。[S-BAr]盐稳定性的提高被认为是由于晶格中非共价相互作用的增加，从而形成了具有理想稳定性特征的固态分子有机金属材料。
