Part I. Synthesis, Characterization, and Reactivity of Low Valent Organotitanium Complexes. Part II. Chemical Vapor Deposition of Rhodium Metal Thin Films PDF Download
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Author: Yujian You Publisher: ISBN: Category : Languages : en Pages :
Book Description
Titanium(II) complex CpTiCl(dmpe)$sb2$ is prepared by reducing (CpTiCl$sb2)sb{rm x}$ with n-butyllithium in the presence of 1,2-bis(dimethylphosphino)ethane (dmpe). Subsequent treatment with methyllithium or n-butyllithium affords CpTiMe(dmpe)$sb2$ and CpTiH(dmpe)$sb2$, respectively. The crystal structures of CpTiX(dmpe)$sb2$ (X = Cl, Me, H) show unusually long metal ligand distances. Analogous treatment of (Cp$sp*$Ti(BH$sb4$)Cl) $sb2$ with n-butyllithium affords Cp$sp*$Ti(BH$sb4$)(PP), where PP is dmpe or (t-butyl)tris(dimethylphosphino-methyl)silane. All of these titanium(II) complexes catalyze oligomerization of ethylene to 1-butene, 2-ethyl-1-butene, and 3-methyl-1-pentene, probably via metallacyclopentane intermediates. Oxidations of the neutral titanium(II) complexes with 1,1$spprime$-dimethylferrocinium salts afford the first examples of cationic alkyltitanium(III) complexes: (CpTiX(dmpe)$sb2rbrack$ BAr$sb4,$ where Ar = Ph or 3,5-(CF$sb3)sb2$C$sb6$H$sb3$ (FPB). Two other complexes, (TiMe$rm sb2(dmpe)sb2rbrack$ FPB and (Cp$sp*$Ti(BH$sb4$)(dmpe)) FPB, have been prepared by oxidation of the corresponding titanium(II) species. Crystallographic studies of (CpTiH(dmpe)$sb2$) FPB, (TiMe$sb2$(dmpe)$sb2$) FPB, and (Cp$sp*$Ti(BH$sb4$)(dmpe)) FPB reveal that the titanium(III) cations show a lengthening of the Ti-P bond distances owing to a decrease in metal-ligand $pi$-back-bonding. The cationic titanium(III) alkyls neither oligomerize nor polymerize ethylene. Treatment of Rh(hfac)(CH$sb2$=CH$sb2)sb2$ (hfac = hexafluoroacetylacetonate) with vinyl-trimethylsilane, 1,2-bis(trimethylsilyl)acetylene, Cu(hfac)(COT), or PMe$sb3$ affords a series of new complexes. High purity rhodium films have been deposited at 200-300 $spcirc$C using Rh(hfac)(CH$sb2$ = CH$sb2)sb2$ as a CVD precursor. The deposition occurs via the disproportionation reaction 3 Rh(hfac)(alkene)$sb2$ $longrightarrow$ 2 Rh + Rh(hfac)$sb3$ + 6 alkene. Ultra high vacuum studies show that Rh(hfac)(CH$sb2$ = CH$sb2)sb2$ adsorbs molecularly on copper surfaces up to 130 K. The hfac groups are oriented perpendicular to the surface at 220 K. Reduction of rhodium(I) occurs at approximately 300 K. Decomposition of surface-bound hfac groups occurs at higher temperatures. This process does not occur under CVD conditions owing to the higher coverages characteristic of this process, which favor bimolecular reactions that lead to the assembly of the observed Rh(hfac)$sb3$ product.
Author: Yujian You Publisher: ISBN: Category : Languages : en Pages :
Book Description
Titanium(II) complex CpTiCl(dmpe)$sb2$ is prepared by reducing (CpTiCl$sb2)sb{rm x}$ with n-butyllithium in the presence of 1,2-bis(dimethylphosphino)ethane (dmpe). Subsequent treatment with methyllithium or n-butyllithium affords CpTiMe(dmpe)$sb2$ and CpTiH(dmpe)$sb2$, respectively. The crystal structures of CpTiX(dmpe)$sb2$ (X = Cl, Me, H) show unusually long metal ligand distances. Analogous treatment of (Cp$sp*$Ti(BH$sb4$)Cl) $sb2$ with n-butyllithium affords Cp$sp*$Ti(BH$sb4$)(PP), where PP is dmpe or (t-butyl)tris(dimethylphosphino-methyl)silane. All of these titanium(II) complexes catalyze oligomerization of ethylene to 1-butene, 2-ethyl-1-butene, and 3-methyl-1-pentene, probably via metallacyclopentane intermediates. Oxidations of the neutral titanium(II) complexes with 1,1$spprime$-dimethylferrocinium salts afford the first examples of cationic alkyltitanium(III) complexes: (CpTiX(dmpe)$sb2rbrack$ BAr$sb4,$ where Ar = Ph or 3,5-(CF$sb3)sb2$C$sb6$H$sb3$ (FPB). Two other complexes, (TiMe$rm sb2(dmpe)sb2rbrack$ FPB and (Cp$sp*$Ti(BH$sb4$)(dmpe)) FPB, have been prepared by oxidation of the corresponding titanium(II) species. Crystallographic studies of (CpTiH(dmpe)$sb2$) FPB, (TiMe$sb2$(dmpe)$sb2$) FPB, and (Cp$sp*$Ti(BH$sb4$)(dmpe)) FPB reveal that the titanium(III) cations show a lengthening of the Ti-P bond distances owing to a decrease in metal-ligand $pi$-back-bonding. The cationic titanium(III) alkyls neither oligomerize nor polymerize ethylene. Treatment of Rh(hfac)(CH$sb2$=CH$sb2)sb2$ (hfac = hexafluoroacetylacetonate) with vinyl-trimethylsilane, 1,2-bis(trimethylsilyl)acetylene, Cu(hfac)(COT), or PMe$sb3$ affords a series of new complexes. High purity rhodium films have been deposited at 200-300 $spcirc$C using Rh(hfac)(CH$sb2$ = CH$sb2)sb2$ as a CVD precursor. The deposition occurs via the disproportionation reaction 3 Rh(hfac)(alkene)$sb2$ $longrightarrow$ 2 Rh + Rh(hfac)$sb3$ + 6 alkene. Ultra high vacuum studies show that Rh(hfac)(CH$sb2$ = CH$sb2)sb2$ adsorbs molecularly on copper surfaces up to 130 K. The hfac groups are oriented perpendicular to the surface at 220 K. Reduction of rhodium(I) occurs at approximately 300 K. Decomposition of surface-bound hfac groups occurs at higher temperatures. This process does not occur under CVD conditions owing to the higher coverages characteristic of this process, which favor bimolecular reactions that lead to the assembly of the observed Rh(hfac)$sb3$ product.
Author: Polly Wanda Chu Publisher: ISBN: Category : Languages : en Pages : 434
Book Description
Thin titanium dioxide films were produced by metalorganic chemical vapor deposition on sapphire(0001) in an ultrahigh vacuum (UHV) chamber. A method was developed for producing controlled submonolayer depositions from titanium isopropoxide precursor. Film thickness ranged from 0.1 to 2.7 nm. In situ X-ray photoelectron spectroscopy (XPS) was used to determine film stoichiometry with increasing thickness. The effect of isothermal annealing on desorption was evaluated. Photoelectron peak shapes and positions from the initial monolayers were analyzed for evidence of interface reaction. Deposition from titanium isopropoxide is divided into two regimes: depositions below and above the pyrolysis temperature. This temperature was determined to be 300 deg C. Controlled submonolayers of titanium oxide were produced by cycles of dosing with titanium isopropoxide vapor below and annealing above 300 deg C. Precursor adsorption below the pyrolysis temperature was observed to saturate after 15 minutes of dosing. The quantity absorbed was shown to have an upper limit of one monolayer. The stoichiometry of thin films grown by the cycling method were determined to be TiO2. Titanium dioxide film stoichiometry was unaffected by isothermal annealing at 700 deg C. Annealing produced a decrease in film thickness. This was explained as due to desorption. Desorption ceased at approximately 2.5 to 3 monolayers, suggesting bonding of the initial monolayers of film to sapphire is stronger than to itself. Evidence of sapphire reduction at the interface by the depositions was not observed. The XPS O is peak shifted with increased film thickness. The shifts were consistent with oxygen in sapphire and titanium dioxide having different O is photoelectron peak positions. Simulations showed the total shifts for thin films ranging in thickness of 0.1 to 2.7 nm to be -0.99 to -1.23 eV. Thick films were produced for comparison.
Author: Manfred T. Reetz Publisher: Springer Science & Business Media ISBN: 3642707041 Category : Science Languages : en Pages : 244
Book Description
Titanium has been used to perform many kinds of reactions in organic and inorganic chemistry. The present book is concerned primarily with a new development in titanium chemistry which is useful in organic synthesis. In 1979/80 it was discovered that the titanation of classical carbanions using C1TiX leads to species with reduced basicity and reactivity. This increases 3 chemo-, regio-and stereo selectivity in reactions with organic compounds such as aldehydes, ketones and alkyl halides. Many new examples have been reported in recent times. Since the nature of the ligand X at titanium can be widely varied, the electronic and steric nature of the reagents is easily controlled. This helps in predicting the stereochemical outcome of many of the C-C bond forming reactions, but the trial and error method is still necessary in other cases. One of the ultimate objectives of chemistry is to understand correlations between structure and reactivity. Although this goal has not been reached in the area of organotitanium chemistry, appreciable progress has been made. A great deal of physical and computational data of organotitanium compounds described in the current and older literature (e. g. , Ziegler-Natta type catalysts) has been reported by polymer, inorganic and theoretical chemists. It is summarized in Chapter 2 of this book, because some aspects are useful in understanding reactivity and selectivity of organo titanium compounds in organic synthesis as described in the chapters which follow.
Author: Ken Tanaka Publisher: John Wiley & Sons ISBN: 3527343644 Category : Science Languages : en Pages : 684
Book Description
An essential reference to the highly effective reactions applied to modern organic synthesis Rhodium complexes are one of the most important transition metals for organic synthesis due to their ability to catalyze a variety of useful transformations. Rhodium Catalysis in Organic Synthesis explores the most recent progress and new developments in the field of catalytic cyclization reactions using rhodium(I) complexes and catalytic carbon-hydrogen bond activation reactions using rhodium(II) and rhodium(III) complexes. Edited by a noted expert in the field with contributions from a panel of leading international scientists, Rhodium Catalysis in Organic Synthesis presents the essential information in one comprehensive volume. Designed to be an accessible resource, the book is arranged by different reaction types. All the chapters provide insight into each transformation and include information on the history, selectivity, scope, mechanism, and application. In addition, the chapters offer a summary and outlook of each transformation. This important resource: -Offers a comprehensive review of how rhodium complexes catalyze a variety of highly useful reactions for organic synthesis (e.g. coupling reactions, CH-bond functionalization, hydroformylation, cyclization reactions and others) -Includes information on the most recent developments that contain a range of new, efficient, elegant, reliable and useful reactions -Presents a volume edited by one of the international leading scientists working in the field today -Contains the information that can be applied by researchers in academia and also professionals in pharmaceutical, agrochemical and fine chemical companies Written for academics and synthetic chemists working with organometallics, Rhodium Catalysis in Organic Synthesis contains the most recent information available on the developments and applications in the field of catalytic cyclization reactions using rhodium complexes.
Author: Yujian You
Author: Yujian You
Author: Yujian You
Author: 
Author: Polly Wanda Chu
Author: Manfred T. Reetz
Author: 
Author: Ken Tanaka
Author: David Christopher Gilmer
Author: Tamara Elizabeth Hanna
Author: LeGrande Mancel Slaughter (III)