High oxidation state organometallic and coordination chemistry: The synthesis and reactivity of nitridoosmium(VI) thiolates and alkoxides
Reinerth, William Alan
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https://hdl.handle.net/2142/22380
Description
Title
High oxidation state organometallic and coordination chemistry: The synthesis and reactivity of nitridoosmium(VI) thiolates and alkoxides
Author(s)
Reinerth, William Alan
Issue Date
1996
Doctoral Committee Chair(s)
Shapley, Patricia A.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Language
eng
Abstract
Transition metal-thioaldehyde complexes were reviewed in Chapter 1. A series of organoosmium(VI) thiolate complexes, (Os(N)$\rm(CH\sb2SiMe\sb3)\sb2(\mu$-SR) $\sb2$ (R = Et, CMe$\sb3,$ CHMe$\sb2,$ CH$\sb2$CHMe$\sb2,$ CH$\sb2$Ph), and the tetraalkoxide and tetrathiolate complexes $\rm\lbrack PPh\sb4\rbrack\lbrack Os(N)(ECH\sb2Ph)\sb4\rbrack$ (E = O, S) were synthesized and characterized. Thermolysis of the tetrathiolate forms benzyl disulfide while the tetraalkoxide complex produces benzaldehyde and benzyl alcohol in a 1:1 ratio upon heating. This first reported example of $\beta$-H elimination from an osmium-alkoxide complex is presented in Chapter 2. The reactivity of the cationic, solvate complex $\rm\lbrack Os(N)(CH\sb2SiMe\sb3)\sb2(NC\sb5H\sb5)\sb2\rbrack\lbrack BF\sb4\rbrack$ with a variety of anionic ligands is reported in Chapter 3. Reactions of this solvate complex with monodentate, anionic ligands yield binuclear or trinuclear complexes, whereas reactions with multidentate and facially-coordinant, anionic ligands, such as indenyl and tris(pyrazolyl)borate, yield mononuclear complexes. The synthesis of several nitridoosmium and nitridoruthenium(VI)-dithiolene complexes is reported in Chapter 4. Included among these are the first organometallic dithiolene complexes possessing multiply-bonded ligands.
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