Download Free Synthesis Structure And Reactivity Of Osmiumvi Nitrido Imido And Oxo Complexes Book in PDF and EPUB Free Download. You can read online Synthesis Structure And Reactivity Of Osmiumvi Nitrido Imido And Oxo Complexes and write the review.

This dissertation, "Crystal Structure Analysis of Imido, Nitrido and Oxo Complexes of Rhenium (V), Osmium (VI) and Ruthenium (III) and Some Complexes of Trinuclear Gold (I)" by 張碧玉, Christine, Cheung Pik-yuk, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b3121021 Subjects: Rhenium Osmium Ruthenium Gold Crystals Transition metal complexes
The tetraphenylphosphonium, bis(triphenylphosphoranylidene)ammonium, and n-butylammonium salts of tetrachlorodioxoosmium were prepared. Alkylation of (PPh$sb4$) (Os(O)$sb2$Cl$sb4$) with trimethylsilylmethylmagnesium chloride yields oxotetrakis(trimethylsilylmethyl)osmium. The crystal structure of Os(O)(CH$sb2$SiMe$sb3$)$sb4$ was determined. The physical properties and reaction chemistry of isoelectronic alkyl complexes of osmium(VI), n-butylammonium nitridotetrakis-(trimethylsilylmethyl)osmium, methylimidotetrakis(trimethylsilylmethyl)osmium, and Os(O)(CH$sb2$SiMe$sb3$)$sb4$ are compared. The nitrido complex does not react with carbon monoxide while both the methyl imide and oxo compounds are reductively carbonylated under CO pressure. The methylimido complex reacts to produce the acyl derivatives, Os(N)(C(O)CH$sb2$SiMe$sb3$)(CH$sb2$SiMe$sb3$)$sb3$ and Os(N)(C(O)CH$sb2$SiMe$sb3$)$sb2$(CH$sb2$SiMe$sb3$)$sb2$. A mono insertion produce is produced in reaction of the methylimide with tert-butylisonitrile. The nitrido complex forms Lewis acid adducts, is alkylated by organic electrophiles, and reacts with mineral acids. Electrophilic cleavage is slower in the methylimido complex while the oxo complex is stable towards electrophiles. The observed differences in reactivity can be ascribed to subtle changes in bonding between the metan and the terminal heteroatom ligand, and to the formation of a structural isomer of the methylimido complex. Pentahaptocyclopentadienylnitridobis(trimethylsilylmethyl)osmium and pentamethylcyclopentadienylnitridobis(trimethylsilylmethyl)osmium can be made from sodium cyclopentadienide or lithium pentamethylcyclopentadienide and n-butylammonium dichlorobis(trimethylsilylmethyl)osmium. The addition of silver tetrafluoroborate to ($etasp5$-C$sb5$H$sb5$)Os(N)(CH$sb2$SiMe$sb3$)$sb2$ formed a silver dimer, ${$ (($etasp5$-C$sb5$H$sb5$)Os($mu$-N)(CH$sb2$SiMe$sb3$)$sb2$) $sb2$Ag$}$(BF$sb4$). The compound reacted with boron trifluoride to form an adduct in solution and with methyltrifluoromethane sulfonate to form the methylimide, (($etasp5$-C$sb5$H$sb5$)Os(NMe)(CH$sb2$SiMe$sb3$)$sb2$) (OSO$sb2$CF$sb3$). The crystal structure of the silver dimer was determined. The phosphine complex, Os(N)Cl(CH$sb2$SiMe$sb3$)$sb2$(PMe$sb3$)$sb2$, was prepared from (N-n-Bu$sb4$) (Os(N)Cl$sb2$(CH$sb2$SiMe$sb3$)$sb2$) and PMe$sb3$. The salt, (Os(N)(CH$sb2$SiMe$sb3$)$sb2$(PMe$sb3$)$sb2$) (BF$sb4$), was prepared by addition of AgBF$sb4$ to the chloride compound. NMR and conductivity studies determined that the chloride compound was neutral while the BF$sb4$ product was cationic. The addition of n-butyl lithium to Os(N)Cl(CH$sb2$SiMe$sb3$)$sb2$(PMe$sb3$)$sb2$ formed n-butylnitrido-bis(trimethylsilylmethyl)osmium.
This dissertation, "Photophysical and Photochemical Properties of Oxo and Nitrido Complexes of Osmium(VI)" by 林曉楓, Hiu-fung, Lam, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b4257649 Subjects: Oxo compounds Osmium compounds Metal ions
Coordination chemistry is the study of compounds formed between metal ions and other neutral or negatively charged molecules. Coordination chemistry includes areas of inorganic solid state chemistry, organometallic chemistry and bioinorganic chemistry, as well as applications to analytical chemistry, catalysis, industrial chemistry and materials science.
When 9 is reacted with single oxygen atom transfer reagents the novel bridging oxo complex in the form of [TpFc,MeFe] 2(μ2-η1:η1-O) (16) is produced. 16 is only the second instance of such a FeII-O-FeII compound to have been isolated and structurally characterized. In the effort to produce additional chalcogenide compounds the complexes TpFc,MeFeOCPh3 (13) and TpFc,MeFeSCPh3 (14) were produced by salt metathesis with 3. The reaction of 14 with KH in the presence of 18-crown-6 to produce a bridging sulfide, [Tp Fc,MeFe]2(μ2-η1:η 1-S) (15). Attempts to produce imide compounds to act as isoelectronic models for terminal oxo compounds by reacting organic azides with 9 and 10 resulted in the production of tetrazene complex TpFc,MeCoN4Bn2 (17), as well as metallated azides TpFc,MeFeN3 (20) and TpFc,MeCoN3 (21).