Organometallic imido, sulfido and oxo complexes of osmium(VI)

Shusta, Jeanine Marie

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Description

Title

Organometallic imido, sulfido and oxo complexes of osmium(VI)

Author(s)

Shusta, Jeanine Marie

Issue Date

1993

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

Transition metal-mediated oxygen, nitrogen, and sulfur transfer reactions to olefins and acetylenes were reviewed in Chapter 1. The alkylosmium(VI) complexes (Y) (Os(N)(R)$\sb2$Cl$\sb2$), Os(N)(CH$\sb2$SiMe$\sb3)\sb2$Cl, Os(N)(CH$\sb2$SiMe$\sb3)\sb2$Cl(NC$\sb5$H$\sb5)$, Os (N)(CH$\sb2$SiMe$\sb3)\sb3$(Z) and (Os(N)(CH$\sb2$SiMe$\sb3)\sb2$(X)$\sb2$) (BF$\sb4$) where Y = NBu$\sp{\rm n}\sb4,$ PPh$\sb4;$ R = CH$\sb2$SiMe$\sb3,$ Me; Z = NC$\sb5$H$\sb5$, PMe$\sb3,$ PPh$\sb3;$ X = NC$\sb5$H$\sb5,$ NCCH$\sb3,$ were synthesized in Chapter 2. Nitrido and imidoosmium(VI) complexes were prepared and their reaction chemistry was studied in Chapter 3. Improved syntheses of $(\eta\sp5$-C$\sb5$H$\sb5$)Os(N)(CH$\sb2$SiMe$\sb3)\sb2$ and $(\eta\sp5$-C$\sb5$Me$\sb5$)Os(N)(CH$\sb2$SiMe$\sb3)\sb2$ where described, while that of $(\eta\sp5$-C$\sb5$H$\sb5$)Os(N)Me$\sb2$ was newly developed. The corresponding imido complexes were prepared using methyl trifluoromethanesulfonate. The imide, (($\eta\sp5$-C$\sb5$H$\sb5$)Os(N)(CH$\sb2$SiMe$\sb3)\sb2$) (OSO$\sb2$CF$\sb3$), was deprotonated with triphenylphosphine, pyridine or water forming $(\eta\sp5$-C$\sb5$H$\sb5$)Os(N=CH$\sb2$)(CH$\sb2$SiMe$\sb3)\sb 2.$ This compound can be reprotonated with strong acids. The reaction of (($\eta\sp5$-C$\sb5$H$\sb5$)Os(N)(CH$\sb2$SiMe$\sb3)\sb2$) (OSO$\sb2$CF$\sb3$) with ethylene produced ($(\eta\sp5$-C$\sb5$H$\sb5$)Os(HN=CH$\sb2$)(C$\sb2$H$\sb4)\sb2$) (OSO$\sb2$CF$\sb3$). Under pressures of ethylene, (($\eta\sp5$-C$\sb5$H$\sb5$)Os(N)(CH$\sb2$SiMe$\sb3)\sb2$) (OSO$\sb2$CF$\sb3$) yielded a nitrogen-containing organic compound. Oxygen- and sulfur-containing osmium(VI) complexes were prepared in Chapter 4. The $\mu\sb3$-sulfidoosmium(VI) cluster (NBu$\sp{\rm n}\sb4$) ((Os(N)(CH$\sb2$SiMe$\sb3)\sb2)\sb3$(S)$\sb2$) was synthesized and its x-ray structure was obtained. The sulfido cluster reacts with (Cu(NCCH$\sb3)\sb4$) (PF$\sb6$) and triphenylphosphine to give a copper-sulfur adduct and triphenylphosphine sulfide. The oxoosmium complex ((Os(N)(CH$\sb2$SiMe$\sb3)\sb2)\sb4$(O)$\sb2$) was synthesized and reacted with triphenylphosphine giving triphenylphosphine oxide. The three complexes ((Os(N)(CH$\sb2$SiMe$\sb3)\sb2$(OH)) $\sb2,$ (NBu$\sp{\rm n}\sb4$) ((Os(N)(CH$\sb2$SiMe$\sb3)\sb3$(OH)) and (NBu$\sp{\rm n}\sb4$) ((Os(N)(CH$\sb2$SiMe$\sb3)\sb2$(OH)$\sb2$) were prepared. Nitridoosmium(VI)amino and amido complexes were synthesized in Chapter 5. The amino complexes included Os(N)(CH$\sb2$Si(CH$\sb3)\sb3)\sb2$(NH$\sb2$CH$\sb3)\sb2$C1, (Os(N)(CH$\sb2$Si(CH$\sb3)\sb3$)$\sb2$(NH$\sb2$CH$\sb3)\sb2$) (BF$\sb4$), (Os(N)Cl$\sb2$(NH$\sb2$CH$\sb3)\sb3$) (Cl), Os(N)(CH$\sb2$SiMe$\sb3)\sb3$(NH$\sb2$Bu$\sp{\rm t})$ and (Os(N)(CH$\sb2$Si(CH$\sb3)\sb3$)$\sb2$(NC$\sb5$H$\sb5$)(NH$\sb2$Bu$\sp{\rm t})$) (BF$\sb4$), while the amido compounds included (NBu$\sp{\rm n}\sb4$) (Os(N)Cl$\sb3$(NHBu$\sp{\rm t}$)) and (NBu$\sp{\rm n}\sb4$) (Os(N)(CH$\sb2$SiMe$\sb3)\sb2$Cl(NHBu$\sp{\rm t}$)).

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Copyright 1993 Shusta, Jeanine Marie

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