Biomimetic Transition Metal Catalysts : Insights from Theoretical Modeling

• The scientific interest in the chemistry of synthetic transition metal complexes is motivated by at least two arguments:1.These can be regarded as models of biological transition metal complexes, e.g. metalloenzymes, whose functions can be difficult to reveal in detail due to their complexity.2.Transition metal complexes are used for catalytic purposes in the industrial synthesis of chemicals. There is a large potential for further development of this technology, which can be motivated both by economic and environmental arguments.In the present thesis, density functional theory (a quantum mechanical method) has been applied to model reactions involving synthetic iron and copper complexes in solution. The complexity of the solvent environment is a challenging problem for theoretical investigations and a significant part of the theses has been to investigate the mechanistic effects of metal-coordinating solvent molecules, Lewis bases and counter ions. For example, it is explained why the cleavage of the O-O bond in heme-diiron-peroxides is faster in the presence of a coordinating Lewis base. Furthermore, the experimentally observed structure-activity relationship between the Fe(III)(µ-O)2Fe(IV) and (H2O)Fe(III)(µ-O)Fe(IV)O motifs is given an explanation. In addition, the present thesis presents a systematic investigation of how the self-interaction error in density functional theory (DFT) affects the modeling of transition metal catalysis.

Subject headings

NATURVETENSKAP  -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)

NATURAL SCIENCES  -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)

Keyword

Catalysis

biomimetic

copper

non-heme iron

heme iron

O2 cleavage

H-atom transfer

radical chemistry

redox chemistry

thermo chemistry

entropy calculations

quantum chemistry

spin states

density functional theory (DFT)

self-interaction error (SIE).

Chemical physics

Kemisk fysik

kemisk fysik

Chemical Physics

Publication and Content Type

vet (subject category)

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