University of Illinois Urbana-Champaign

Synthesis and reactivity of organometallic nitridoosmium(VI), ruthenium(VI) complexes

Zhang, Naijie

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Description

Title
Synthesis and reactivity of organometallic nitridoosmium(VI), ruthenium(VI) complexes
Author(s)
Zhang, Naijie
Issue Date
1991
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
  • Chemistry, Organic
Language
eng
Abstract
  • New organometallic osmium(VI) complexes with sulfur and oxygen containing ligands, (Os(N)(CH$\sb2$SiMe$\sb3)\sb2$Y) $\sp-$ $\{$Y = (SCH$\sb2$CH$\sb2$S), (SCN)$\sb2$, (S), (S-C$\sb5$H$\sb4$N), (WS$\sb4$), (MoS$\sb4$), (SO$\sb4$), (CO$\sb3$), (ReO$\sb4)\sb2\}$ were prepared. Two crystal structures of (Os(N)(R)$\sb2$(SC$\sb5$H$\sb4$N)) $\sb2$, (NBu$\sp{\rm n}\sb4$) (Os(N)(R)$\sb2$(WS$\sb4$)) (R = CH$\sb2$SiMe$\sb3)$ were determined.
  • The first osmium and ruthenium alkyl complexes containing bidentate chromate group (NBu$\sp{\rm n}\sb4$) (M(N)(CH$\sb2$SiME$\sb3)\sb2$(CrO$\sb4$)) (M = Os, Ru) were synthesized by the reaction of (M(N)R$\sb2$Cl$\sb2$) $\sp-$ with Ag$\sb2$CrO$\sb4$ or K$\sb2$CO$\sb4$ in high yields. A crystal structure of (NBu$\sp{\rm n}\sb4$) (Ru(N)(CH$\sb2$SiMe$\sb3)\sb2$(CrO$\sb4$)) was determined. All of the osmium and ruthenium complexes are thermally stable to air and water and soluble in organic solvents.
  • The osmium and ruthenium chromate complexes, cis- (NBu$\sp{\rm n}\sb4$) (M(N)(CH$\sb2$SiMe$\sb3)\sb2$CrO$\sb4$) (M = Ru, Os) are catalysts for selective oxidation of alcohols to the corresponding carbonyl compounds under mild conditions with molecular oxygen as a secondary oxidant. Kinetic and mechanistic studies were carried out on the oxidation of benzyl alcohol by cis- (NBu$\sp{\rm n}\sb4$) (Os(N)(CH$\sb2$SiMe$\sb3)\sb2$CrO$\sb4$). The reaction is first order in both cis- (NBu$\sp{\rm n}\sb4$) (Os(N)(CH$\sb2$SiMe$\sb3)\sb2$CrO$\sb4$) and O$\sb2$ and zero order in alcohol. Dioxygen labelling studies show that the $\sp{17}$O$\sb2$is incorporated into the bridge oxo of cis- (NBu$\sp{\rm n}\sb4$) (Os(N)(CH$\sb2$SiMe$\sb3)\sb2$CrO$\sb4$). The most likely mechanism for the oxidation of alcohols by cis- (NBu$\sp{\rm n}\sb4$) (Os(N)(CH$\sb2$SiMe$\sb3)\sb2$CrO$\sb4$) involves a concentrated $\beta$-hydrogen elimination and oxygen insertion as a rate-determining step.
Type of Resource
text
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Copyright and License Information
Copyright 1991 Zhang, Naijie

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