Selectivity of Rh⋅⋅⋅H-C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State.

ABSTRACT: Single-crystal to single-crystal solid-state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of the σ-alkane complex [Rh(tBu₂ PCH₂ CH₂ CH₂ PtBu₂ )(η² ,η² -C₇ H₁₂ )][BAr^F ₄ ] (Ar^F =3,5-(CF₃ )₂ C₆ H₃ ), in which the alkane (norbornane) binds through two exo-C-H⋅⋅⋅Rh interactions. In contrast, the bis-cyclohexyl phosphine analogue shows endo-alkane binding. A comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, traces this different regioselectivity to subtle changes in the local microenvironment surrounding

SUBMITTER: Furfari SK 

PROVIDER: S-EPMC7898853 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature