High oxidation state organometallic and coordination chemistry: The synthesis and reactivity of nitridoosmium(VI) thiolates and alkoxides

Transition metal-thioaldehyde complexes were reviewed in Chapter 1. A series of organoosmium(VI) thiolate complexes, (Os(N)\rm(CH\sb2SiMe\sb3)\sb2(μ-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 β-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.

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

2011

Author dc:creator

• Reinerth, William Alan

Contributors dc:contributor

• Shapley, Patricia A.

• Chemistry, Inorganic

Statement dc:rights

• Copyright 1996 Reinerth, William Alan

Language dc:language

eng

Identifier

9780591088366
AAI9702651
(UMI)AAI9702651

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/22380