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Author: Robert William Marshman Publisher: ISBN: Category : Languages : en Pages : 352
Book Description
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.
Author: Robert William Marshman Publisher: ISBN: Category : Languages : en Pages : 352
Book Description
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.
Author: 林曉楓 Publisher: Open Dissertation Press ISBN: 9781374698062 Category : Languages : en Pages :
Book Description
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
Author: 張碧玉 Publisher: Open Dissertation Press ISBN: 9781374742178 Category : Languages : en Pages :
Book Description
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
Author: J. A. McCleverty Publisher: Newnes ISBN: 0080913164 Category : Science Languages : en Pages : 11845
Book Description
Comprehensive Coordination Chemistry II (CCC II) is the sequel to what has become a classic in the field, Comprehensive Coordination Chemistry, published in 1987. CCC II builds on the first and surveys new developments authoritatively in over 200 newly comissioned chapters, with an emphasis on current trends in biology, materials science and other areas of contemporary scientific interest.
Author: Jeanine Marie Shusta Publisher: ISBN: Category : Languages : en Pages : 472
Book Description
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$sp{rm t}$)).
Author: Claudio Pettinari Publisher: Imperial College Press ISBN: 1860948774 Category : Science Languages : en Pages : 570
Book Description
Since their discovery by Swiatoslaw Trofimenko in 1967, poly(pyrazol-1-yl)borates have been considered as one of the most useful ligands in modern coordination chemistry. The term OC scorpionateOCO has been used to describe the interchange between bidentate and tridentate coordination modes by these ligands that has been employed for the synthesis of complexes with virtually every metal in the periodic table, having applications in diverse fields ranging from homogeneous catalysis to bioinorganic chemistry.This all-inclusive reference book continues where Trofimenko''s original work left off. It not only includes discussions on all new ligands reported from 1999 to date, but also introduces new ligands that have yet to be touched upon in other titles, such as scorpionates based on S donors or P donors. As such, this comprehensive volume is a OC must haveOCO for all researchers who utilize this family of molecules."
Author: Claudio Pettinari Publisher: World Scientific ISBN: 1908979070 Category : Science Languages : en Pages : 570
Book Description
Since their discovery by Swiatoslaw Trofimenko in 1967, poly(pyrazol-1-yl)borates have been considered as one of the most useful ligands in modern coordination chemistry. The term “scorpionate” has been used to describe the interchange between bidentate and tridentate coordination modes by these ligands that has been employed for the synthesis of complexes with virtually every metal in the periodic table, having applications in diverse fields ranging from homogeneous catalysis to bioinorganic chemistry.This all-inclusive reference book continues where Trofimenko's original work left off. It not only includes discussions on all new ligands reported from 1999 to date, but also introduces new ligands that have yet to be touched upon in other titles, such as scorpionates based on S donors or P donors. As such, this comprehensive volume is a “must have” for all researchers who utilize this family of molecules./a
Author: Robert William Marshman
Author: Robert William Marshman
Author: Jennifer Lynn Koch
Author: 林曉楓
Author: 張碧玉
Author: J. A. McCleverty
Author: Jeanine Marie Shusta
Author: Jon A. McCleverty
Author: 
Author: Claudio Pettinari
Author: Claudio Pettinari