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)$\rm(CH\sb2SiMe\sb3)\sb2(\mu$-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.U of I OnlyETDs are only available to UIUC Users without author permissio