Журнал физической химии и биофизики
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Solid-State NMR Crystallography: from Catalytic Active Complexes to Enzymes

Gerd Buntkowsky

Despite the tremendous importance of catalysis for all types of chemistry and biochemistry, there is still a huge gap
in detailed knowledge of the processes and reaction intermediates on the surfaces of the catalysts or inside. The
combination of conventional and Dynamic Nuclear Polarization (DNP) enhanced solid-state NMR spectroscopy,
x-ray diffraction, electron microscopy, chemical modelling and quantum chemical calculations, often loosely
summarized as NMR crystallography, has evolved into one of the most powerful characterization tools to fill this gap
and study solid catalysts and chemical processes on their surface or the active center of an enzyme. These techniques
give an unprecedented view in the chemistry of immobilized homogeneous transition metal catalysts, supported
e.g. on silica or crystalline nanocellulose (CNC) or polymer based core shell structures as carriers or reactants and
reaction intermediates on transition metal nanoparticles (MNPs). The contribution presents recent examples from
our group about solid-state NMR spectroscopic characterizations of mono- or binuclear Rhodium, Ruthenium and
Iridium catalysts and a Nickel containing enzyme. The focus is set to the immobilization of Wilkinsons’s type
catalyst and the dirhodium-acetate dimer (Rh2ac4). These are linked covalently to high-surface silica or crystalline
nanocellulose support materials, employing amine, phosphine, pyridyl or carboxyl functions on the surface of the
support materials or mesoporous silica supports. Combinations of 13C-, 15N-, 29Si- and 31P- CP MAS, J-resolved
31P- MAS and HETCOR solid-state NMR techniques are employed to monitor the preparation of the catalyst.
Moreover, by DNP enhanced solid-state NMR it is feasible to detect different carboxyl and amine binding sites in
natural abundance at a fast time scale.