Mechanistic Studies of the Chemical Vapor Deposition of Ceramic and Metal Films From Organometallic Precursors

Investigations of the thermolysis of tetra(neopentyl)titanium (TiNp$\sb4$) in solution have been carried out in parallel with studies of the chemical mechanism responsible for its conversion to titanium carbide under CVD conditions. A kinetic isotope effect (k\sb{\rmα (H)}/k\sb{\rmα (D)} = 5.2 \pm 0.4) upon deuterating the alkyl groups at the α positions provides clear evidence that the initial step in the thermolysis is an α-hydrogen elimination reaction to form neopentane. The activation parameters for this α-hydrogen elimination process are $\rm\Delta H\sp\ddagger = 21.5 \pm 1.4$ kcal/mol and $\rm\Delta S\sp\ddagger = -16.6 \pm 3.8$ cal/mol K.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Cheon, Jinwoo

Contributors dc:contributor

• Girolami, Gregory S.

• Chemistry, Inorganic

Identifier

(UMI)AAI9411588

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/72288