Organometallic Imido Sulfido And Oxo Complexes Of Osmium Vi

Download or read book Organometallic Imido, Sulfido and Oxo Complexes of Osmium (vi) written by Jeanine Marie Shusta and published by . This book was released on 1993 with total page 472 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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 $(etasp5$-C$sb5$H$sb5$)Os(N)(CH$sb2$SiMe$sb3)sb2$ and $(etasp5$-C$sb5$Me$sb5$)Os(N)(CH$sb2$SiMe$sb3)sb2$ where described, while that of $(etasp5$-C$sb5$H$sb5$)Os(N)Me$sb2$ was newly developed. The corresponding imido complexes were prepared using methyl trifluoromethanesulfonate. The imide, (($etasp5$-C$sb5$H$sb5$)Os(N)(CH$sb2$SiMe$sb3)sb2$) (OSO$sb2$CF$sb3$), was deprotonated with triphenylphosphine, pyridine or water forming $(etasp5$-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 (($etasp5$-C$sb5$H$sb5$)Os(N)(CH$sb2$SiMe$sb3)sb2$) (OSO$sb2$CF$sb3$) with ethylene produced ($(etasp5$-C$sb5$H$sb5$)Os(HN=CH$sb2$)(C$sb2$H$sb4)sb2$) (OSO$sb2$CF$sb3$). Under pressures of ethylene, (($etasp5$-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 $musb3$-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$sp{rm t}$)).