Adaptivity in Solid-State Molecular Organometallic Chemistry

Chapter 1: This chapter introduces the topics pertinent to this thesis, including: in-crystallo chemistry; single-crystal to single-crystal transformations; σ-complexes; and C-H activation by organometallic complexes.
Chapter 2: This chapter reports on the in-crystallo reactivity of [M(R-PONOP)(L)(CO)2][BArF4] complexes with carbon monoxide. The reaction of these complexes with CO gas is shown to produce significant alterations to the 2° microenvironment and 3° periodic structure. Periodic DFT calculations are utilised
to understand the non-covalent interactions responsible for these results. The use of MicroED techniques to circumvent crystal-cracking in SCSC transformations is also discussed.
Chapter 3: This chapter reports on the in-crystallo synthesis, characterisation, and onward reactivity of a highly reactive, but stable, Rh(III) η1-σ-alkane complex, supported by a structurally-responsive ligand. The structural-response of the ligand framework is shown to be reversible through substitution of the σ-alkane
with propylene. The ligand framework is also shown to facilitate selective H/D exchange at unactivated alkyl C-H positions.