Heidelberg, Univ., Diss., 2007. / Online publiziert: 2008.

Heidelberg, Univ., Diss., 2008.

Techn. Univ., Diss.--Braunschweig, 2003.

Thesis--Göteborg. / In Periodical Room.

Thesis (doctoral)--Freie Universität Berlin, 1983.

Techn. University, Diss., 2005--München.

Zugl.: Stuttgart, Univ., Diss., 2009

Techn. Universiẗat, Diss., 2003--Clausthal.

Olefin metathesis is a powerful tool for assembly of carbon-carbon bonds. Amines and related N-donors are problematic functional groups in Ru-catalyzed olefin metathesis - a well- documented, but poorly understood problem. The first part of this thesis focuses on amine-induced deactivation pathways; two of which are described in depth. Alkylidene abstraction, a previously unknown reaction for nitrogen nucleophiles, was observed for smaller and less Bronsted-basic amines. Deprotonation of the metallacyclobutane intermediate formed during catalysis is prominent for highly Bronsted basic or sterically bulky N-donors. Monosubstituted (and, by extension unsubstituted) metallacyclobutanes are particularly vulnerable to deprotonation. For each pathway, the fate of the alkylidene Ru=CHR functional group proved key in determining the nature of deactivation. Both pathways have been detected during catalysis, as evidenced by formation of diagnostic amine (RCH2NR2’) or substituted propene products. A combination of quantitative NMR and GC-MS analysis was used to identify these species on loss of the Ru-alkylidene functional group. The second part of this thesis focuses on incorporating amines into catalyst design – an under-utilized strategy in the context of Ru-catalyzed olefin metathesis. A modified Grubbs-type catalyst was developed featuring a bulky, relatively non-basic biaryldiamine ligand. Metathesis activity for this catalyst was comparable, and in some cases superior to the most widely-used homogeneous catalysts currently available. Several new, related Ru-benzylidenes were also prepared and fully characterized in conjunction with the mechanistic studies described above. Progress toward development of N-anion-containing metathesis catalysts is also discussed. Synthesis of Ru-hydride complexes originally intended for this purpose allowed for a fundamental study of the coordination chemistry and reductive elimination chemistry of the NPh2– anion.

Solid porous materials are network materials that contain space void. Porous Organic Polymers (POPs) are porous materials, which are constructed from organic building blocks and exhibit large surface area with low densities. Due to these characteristics, POPs have attracted attentions because of their potential use in application such as gas storage and chemical separation. This thesis presents a study of the synthesis of novel POP being a network based on 2,5- dibromobenzaldehyde and 1,3,5-triethynylbenzene linked together via Sonogashira- Hagihara (SH) coupling. This network showed a relatively good surface area of 770 m2/g and total pore volume of 0.59 cc/g. In addition, it proved to be chemically and thermally stable, maintaining the thermal stability up to 350oC. In addition to synthesize novel aldehyde-POP network, it was also possible to post synthetically modify a network via one-step post synthetic functionalization by amine. Ethelynediamine (EDA), Diethylenetriamine (DETA), and Tris(2-aminoethyl)amine (Tris-amine) are three different amines used for aldehyde-POP functionalization. The produced networks were aminated via different amine species substitution the aldehyde group present within the network. Modification to these networks resulted in a decrease in surface area from 770 m2.g-1 to 333 m2.g-1, 162 m2.g-1, and 211 m2.g-1 in respective to EDA, DETA, and Tris-amine. Although the surface areas were decreased, the CO2 adsorption was enhanced as evidenced by the increase of Qst (i.e., from 25 to 45 kJ.mol-1 for DETA at low coverage). Our findings are expected to strengthen existing research areas of the influence of different type of amines (e.g aromatic amine) on CO2 adsorption. Although amine grafting has been studied in other systems (e.g., PAFs and MOFs), we are the first to reported amine functionalized POPs using a novel one-step amine grafting PSM procedure. Future research might extend to study the interaction between CO2 and amine species under real working conditions.