Publication Date

2013-11-13

Availability

Open access

Embargo Period

2014-11-13

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PHD)

Department

Chemistry (Arts and Sciences)

Date of Defense

2013-11-07

First Committee Member

Burjor Captain

Second Committee Member

Carl D. Hoff

Third Committee Member

Jamie D. Walls

Fourth Committee Member

Ali Ghahremaninezhad

Abstract

In past years bimetallic nanoparticle catalysts have been shown to exhibit superior catalytic properties, due to the presence of different metals such that one metal performs a certain role in a catalytic cycle and the other performs another function. Our goal was to synthesize bimetallic cluster complexes containing cheap metals for the application in heterogeneous catalysis. We have reported the reaction of Fe5(C)(CO)15 with Ni(COD)2, in acetonitrile solvent to afford the nickel-iron complex NiFe5(C)(NCMe)(CO)15. In addition, some chemistry with this compound was studied which gave new Fe-Ni carbide clusters with varying Fe-Ni ratios. Similar chemistry was observed with the reaction of Ru5(C)(CO)15 with Ni(COD)2. Electronic unsaturation in transition metal complexes is induced by bulky ligands. The bulky ligands shield the metal center from the approach of large molecules, leaving enough room for the selective approach of small molecules. Bulky ligands such as phosphines, stananes, germanes and N-heterocyclic carbenes stabilize the reactive intermediates of transition metal complexes. Based on this approach, we have synthesized Ru-Ge cluster complexes from the reaction of bulky tertiary butyl germane, ButGeH3 with ruthenium carbonyl complexes. We have also synthesized Ru-Pt bimetallic transition metal cluster complexes with bulky N-heterocyclic carbene ligand. All the new compounds were structurally characterized by single-crystal X-ray diffraction analyses.

Keywords

Bimetallic cluster; Transition metal; Tertiary butyl germane; N-heterocyclic carbene; Heterogeneous catalysis; Small molecule activation

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