The self-metathesis reaction of 1-octene with several well-known Grubbs-type precatalysts and the new Z-selective Grubbs precatalyst were studied with molecular modeling. The obtained Gibbs-free energy values for all the steps during the productive metathesis of 1-octene were compared to the values obtained for some low catalytic activity precatalysts. Determining how the Gibbs-free energy values of highly active precatalysts compare to that of low catalytic activity precatalysts gave a deeper insight into the mechanism. The questionable correlation of the theoretically observed trends with those obtained experimentally does point to the need to be very cautious when making assumptions from theoretical results without a sufficiently large dataset.

The productive self-metathesis reaction of 1-octene in the presence of the Phobcat precatalyst [RuCl(2)(Phoban-Cy)(2)(=CHPh)] using density functional theory was investigated and compared to the Grubbs 1 precatalyst [RuCl(2)(PCy(3))(2)(=CHPh)]. At the GGA-PW91/DNP level, the geometry optimization of all the participating species and the PES scans of the various activation and catalytic cycles in the dissociative mechanism were performed. The formation of the catalytically active heptylidene species is kinetically and thermodynamically favored, while the formation of trans-tetradecene is thermodynamically favored.

The productive self-metathesis of 1-octene with a series of new phosphine ligated Grubbs-type precatalysts was studied. The resulting structures were used to compare some steric properties of the new precatalysts with those of well-known precatalysts. The possibility of α-CC agnostic stabilization as well as the ability of the ligands to shield the metal was studied. A comparison of the obtained data, pointed to the unlikelihood that α-CC agostic stabilization is a major contribution to the stabilization of the various metallacyclobutane rings. The similarity in the ability of the ligands to shield the metal also raised questions about the comparison of experimentally observed trends with those obtained theoretically.

Sedert die ontdekking van die ruteniumbevattende prekatalisatore, Grubbs 1 (1) en Grubbs 2 (2), is ’n toename in die ontwikkeling van soortgelyke prekatalisatore getoon. Daar is egter nie met die karakterisering van die prekatalisatore met behulp van kernmagnetieseresonansiespektrometrie (KMR) tred gehou nie. Die gerapporteerde KMR-analises en -karakterisering is meestal tot 1H-, 31P-, COSY-analise beperk met seldsame vermelde 13C-analise. Die hoë natuurlike isotoopvoorkoms van 1H- en 31P-kerne, 99.98% en 100% onderskeidelik, is ’n bydraende faktor tot die vinnige en eenvoudige opname van hierdie spektra. Die leemte in literatuurdata en- opnameparameterstelle aangaande 13C-KMR-analise, word aan die lae natuurlike isotoopvoorkoms van 13C-kerne (1.10%) en die ingeperkte stabiliteit van die katalisatore in oplossing toegeskryf. In hierdie ondersoek is prekatalisator 1 gebruik om ’n KMR-parameterstel te ontwikkel. Daarna is twee verdere kommersiële Grubbs-tipe-prekatalisatore, 2 en 3, met behulp van hierdie KMR-parameterstel geanaliseer. Die KMR-spektra is weens die lang opnametyd en die onstabiliteit van die prekatalisatore in oplossing in drie stappe opgeneem. Eerstens, is 1H-, COSY-, HSQC- en HMBC-spektra opgeneem, wat altesaam vier ure geduur het. Tweedens, is DEPT135-spektra opgeneem, wat drie ure in beslag geneem het. Laastens is die 13C-spektra opgeneem waarvoor 7 ure in beslag geneem is. Die KMR-parameterstel wat vanaf die kommersiële prekatalisatore afgelei is, is gevolglik aangewend om ses verdere gesintetiseerde, nie-kommersiële Grubbs-tipeprekatalisatore, 4 tot 9, gedeeltelik te karakteriseer. Deur die voorkoms van oorvleuelende pieke in die aromatiese en alifatiese gebiede is die spektrumresolusie verlaag. Gevolglik is die volledige karakterisering nie moontlik gemaak nie.