Lewis, Nathan Saul (1977) The chemistry of rhodium and molybdenum isocyanide complexes. Master's thesis, California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-09192007-110805
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The rhodium isocyanide dimer, [...], has been synthesized and characterized. Like monomeric rhodium isocyanide complexes, the dimer has a tendency to associate in solution and reversibly form oligomers. These oligomers have been detected spectroscopically, and concentration dependences verify their formulation as high aggregates. The dimer also undergoes two-center, two-electron oxidative addition with a variety of reagents, including the halogens, methyl iodide, ethyl iodide, and methyl tosylate. These oxidative adducts have been characterized and studied through a variety of techniques. The dimer, unlike rhodium isocyanide monomers, acts as a base and binds one proton in aqueous solution. Titration data are presented, and an approximate [...] has been obtained. When treated with aqueous acid, visable light (546 nm) photolysis of solutions of [...] yields molecular hydrogen with quantum yields as high as 0.04. The photochemistry is oxygen sensitive, as well as anion dependent. Possible means of exploiting the photoreaction in a solar energy storage scheme is also discussed. In order to better understand the metal-metal interactions in the dimeric species, extended-Huckel molecular orbital calculations were performed on the rhodium dimer, as well as on monomeric fragments with the four isoelectronic metals Ru(O), Pd(II), Co(I), and Ir(I). These results, and their relationship to observed physical properties of the rhodium dimer are discussed in detail.
|Item Type:||Thesis (Master's thesis)|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||31 May 1977|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||17 Oct 2007|
|Last Modified:||26 Dec 2012 03:01|
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