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Activation Of Carbon Hydrogen Bonds Mediated By Ruii Complexes
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Book Synopsis Activation of Carbon-hydrogen Bonds Mediated by Ru(II) Complexes by : Karl Ashley Pittard
Download or read book Activation of Carbon-hydrogen Bonds Mediated by Ru(II) Complexes written by Karl Ashley Pittard and published by . This book was released on 2007 with total page 152 pages. Available in PDF, EPUB and Kindle. Book excerpt: Keywords: heteroaromatic compounds, C-H Activation.
Book Synopsis Activation of Carbon-Hydrogen Bonds Mediated by Ru(II) Complexes by :
Download or read book Activation of Carbon-Hydrogen Bonds Mediated by Ru(II) Complexes written by and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The RuII complex TpRu(CO)(NCMe)Me (Tp = hydridotris(pyrazolyl)borate) initiates carbon-hydrogen bond activation at the 2-position of furan and thiophene to produce methane and TpRu(CO)(NCMe)Ar (Ar = 2-furyl or 2-thienyl). Solid-state structures have been determined for TpRu(CO)(NCMe)(2-thienyl) and [TpRu(CO)(m-C, S-thienyl)]2. The complex TpRu(CO)(NCMe)(2-furyl) serves as a catalyst for the formation of 2-ethylfuran from ethylene and furan. Similar catalytic reactivity was observed with TpRu(CO)(NCMe)(2-thienyl) for the production of 2-ethylthiophene. Density functional theory (DFT) calculations of the C-H activation of furan by {(TAB)Ru(CO)Me} (TAB = tris(azo)borate) indicate that the C-H activation sequence does not proceed through a RuIV oxidative addition intermediate. The reaction of TpRu(CO)(NCMe)Me and pyrrole forms TpRu(CO){k 2-N, N-(H)N=C(Me)(NC4H3)}. The formation of complex TpRu(CO){k2-N, N-(H)N=C(Me)(NC4H3)} involves the cleavage of the N-H bond and 2-position C-H bond of pyrrole as well as a C-C bond forming step between pyrrole and the acetonitrile ligand of {TpRu(CO)(NCMe)}. Mechanistic studies indicate that the most likely reaction pathway involves initial metal-mediated N-H activation of pyrrole to produce TpRu(CO)(NCMe)(N-pyrrolyl) followed by C-C bond formation and proton transfer. Complex TpRu(CO)(NCMe)(N-pyrrolyl) has been independently prepared. At elevated temperatures, TpRu(CO)(NCMe)(N-pyrrolyl) converts to TpRu(CO){k2-N, N-(H)N=C(Me)(NC4H3)}. Single crystal X-ray analysis has been achieved for TpRu(CO)(NCMe)(N-pyrrolyl), [TpRu(CO)(NCMe)(h1-O-OC4H8) and TpRu(CO){k2-N, N-(H)N=C(Me)(NC4H3)}. Computational studies support the suggested selectivity for initial N-H bond cleavage in preference to C-H bond activation. Rational design for a more electron-poor hydroarylation catalyst was discussed. Synthesis of Mp (Mp = tris(pyrazolyl)methane) complexes of the type [MpRu(PPh3)(CO)H]BAr'4, [MpRu(PPh3)(CO)Cl]BAr'4].
Book Synopsis Transition Metal-mediated Carbon-heteroatom Bond Activation by : Aaron Patrick Walsh
Download or read book Transition Metal-mediated Carbon-heteroatom Bond Activation written by Aaron Patrick Walsh and published by . This book was released on 2015 with total page 391 pages. Available in PDF, EPUB and Kindle. Book excerpt: "Two transition metal-mediated systems were studied to understand6 the dominant and fundamental factors involved in controlling the reactivity of activation of relatively strong carbon-heteroatom bonds. The metal arene dimeric complex, [Cp*RhCl2]2, was used to facilitate ortho-directed carbon-hydrogen bond activation with the assistance of the exogenous organic base sodium acetate and derivatives thereof to explore the influence of pKa on the concerted metalation-deprotonation pathway and the implications the effect has in the overall cyclometalation of the substrate. In general, the cyclometalation of 2-(4-methoxyphenyl)pyridine by [Cp*RhCl2]2 is affected by two characteristics of the carboxylate additive: the pKa and steric bulk. In this study we sought to explore the ability of [Cp*RhCl2]2, and similar species, such as [Cp*IrCl2]2 and [(p-cymene)RuCl2]2, to activate carbon-hydrogen bonds of ortho-alkylated aromatic isocyanides by electrophilic means via the concerted metalation-deprotonation pathway. Eighteen new electrophilic metal-isocyanide complexes were synthesized and fully characterized. Isocyanide induced cleavage of the dimer, [LMCl2]2 {LM = Cp*Ir, Cp*Rh, or (p-cymene)Ru}, with 2,6-xylylisocyanide or 2,6-diethylphenylisocyanide produced complexes of the general formula LM(CNAr)Cl2. Halide metathesis of the dichloride complexes with sodium iodide produced the corresponding complexes with the general formula LM(CNAr)I2. For the analogous ruthenium complexes better results were achieved via isocyanide induced cleavage of [(p-cymene)RuI2]2. From these neutral complexes, reaction with AgPF6 in acetonitrile gave cationic, solvent-coordinated complexes that are chiral-at-metal. They have been fully characterized and crystallize as racemates. Reactions with rhodium gave either the previously unreported [Cp*RhCl(MeCN)]2[(PF6)2] when starting from Cp*Rh(CNAr)Cl2, or [Cp*Rh(MeCN)3][(PF6)2] and Cp*Rh(CNAr)I2 when starting from Cp*Rh(CNAr)I2. Several bases were probed to see if C-H activation at a benzylic position to create a novel metallacycle could be induced, but were not successful in any case. The other system studied the reactivity of the {(dippe)Pt0} (dippe = (iPr)2PCH2CH2P(iPr)2) fragment with carbon-chalcogenide bonds and mechanistic pathways that could be involved in cleaving these bonds and subsequent reactions that occur to account for the observed products. The precursor complex, (dippe)Pt(NBE)2 (NBE = norbornene), oxidatively adds both carbon-sulfur and carbon-oxygen bonds. In the case of carbon-sulfur bond activation the platinum fragment reacts with cyclic and linear thioethers, upon heating, to give oxidative addition products. Further heating leads to disproportionation and concomitant formation of desulfurized organic by-products and platinum-bisthiolate complexes, (dippe)Pt(SR)2, in several cases. Furthermore, the platinum fragment also oxidatively adds a variety of esters upon heating in which the less reactive, ether carbon-oxygen bond is cleaved to yield alkyl-, and aryl-platinum carboxylates, (dippe)Pt(OCOR)2. Further heating, again, leads to disproportionation and concomitant formation of deoxygenated organic by-products and platinum-biscarboxylate."--Pages vii-viii.
Book Synopsis Transition-metal Mediated Formation and Cleavage of Carbon-hydrogen Bonds by : Paul Fredrich Seidler
Download or read book Transition-metal Mediated Formation and Cleavage of Carbon-hydrogen Bonds written by Paul Fredrich Seidler and published by . This book was released on 1985 with total page 384 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Selective Carbon-hydrogen Bond Activation of Unfunctionalized Hydrocarbons with Substituted Zirconocence Imido Complexes by : Helen McAdams Hoyt
Download or read book Selective Carbon-hydrogen Bond Activation of Unfunctionalized Hydrocarbons with Substituted Zirconocence Imido Complexes written by Helen McAdams Hoyt and published by . This book was released on 2007 with total page 512 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis The Investigation of Carbon-hydrogen Bond Activation by a Rhodiumtrispyrazolylborate Complex by : Andrew James Vetter
Download or read book The Investigation of Carbon-hydrogen Bond Activation by a Rhodiumtrispyrazolylborate Complex written by Andrew James Vetter and published by . This book was released on 2005 with total page 512 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Meeting the Challenges by : Hongwang Wang
Download or read book Meeting the Challenges written by Hongwang Wang and published by . This book was released on 2009 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: My thesis is divided into two parts. The first part is focused on studies of N-heterocyclic carbene (NHC) palladium(IV) intermediates, which are involved in oxidative addition mediated C-C, and C-O bond formation processes as well as in C-Cl bond forming reactions via a reductive elimination process. Bis-NHC-Pd(II) complexes have been reported as effective catalysts to mediate direct conversion of methane into methanol. However, a H-D exchange study revealed that the bis-NHC-Pd(II) complexes are not the active species responsible for the C-H bond activation reaction. This unexpected result implies that the high oxidation state bis- NHC-Pd(IV) species may be the real catalyst! The oxidative addition of methyl iodide to the bis- NHC-Pd(II)-Me2 complex led to the successful observation of the formation of a transient trimethyl bis-NHC-Pd(IV) intermediate by both 1H-NMR and 13C-NMR spectroscopy. Different oxidants such as O2, PhI(OAc)2, PhI(OTFA)2 and Cl2 reacted with the bis-NHC-Pd(II)-Me2 complex, and competitive C-C and C-O bond formations, as well as C-C and C-Cl bond formations were observed. Dioxygen triggered C-C bond formation under dry condition and both C-C and C-O bond formation in the presence of H2O gave strong indications that the bis-NHCPd(II)-Me2 complex can be oxidized to a bis-NHC-Pd(IV) intermediate by dioxygen. The reaction between the hypervalent iodine regents PhI(OAc)2 and PhI(OTFA)2 and the bis-NHCPd(II)-Me2 complex gave only reductive elimination products. Therefore, this system can act as a model system, which is able to providing valuable information of the product forming (functionalization) step of the C-H bond activation system. The reaction between chlorine and the bis-NHC-Pd(II)-Me2 complex resulted in a relatively stable bis-NHC-Pd(IV)-Cl4 complex, which was characterized by 1H-NMR spectroscopy and mass spectroscopy. The structure of bis- NHC-Pd(IV)-Cl4 was unambiguously established by X-ray crystallography. The second part of this thesis describes the synthesis of functionalized bimagnetic core/shell iron/iron oxide nanoparticles for the treatment of cancer. Biocompatible dopamineoligoethylene glycol functionalized bimagnetic core/shell Fe/Fe3O4 nanoparticles were prepared via ligand exchange, and purified by repeated dispersion/magneto-precipitation cycles. A porphyrin (TCPP) has been tethered to the stealth nanoparticles to enhance their uptake by tumor cells and (neural) stem cells. The stealth nanoparticles have been delivered in a mouse model to tumor sites intravenously by using the EPR (enhanced permeation and retention) effect. Magnetic hyperthermia proved to be very effective against B16-F10 mouse melanomas in Charles River black mice. After hyperthermia, the nanoparticles have shown a significant effect on the growth of tumor (up to 78% growth inhibition).
Book Synopsis The Mechanism of Carbon-hydrogen Bond Activation with Hard-ligated Rhodium Complexes by : Chunming Wang
Download or read book The Mechanism of Carbon-hydrogen Bond Activation with Hard-ligated Rhodium Complexes written by Chunming Wang and published by . This book was released on 1994 with total page 264 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Carbon-hydrogen Bond Activation and Related Reactions Involving Early Metal Amido and Imido Complexes by : Chris Patrick Schaller
Download or read book Carbon-hydrogen Bond Activation and Related Reactions Involving Early Metal Amido and Imido Complexes written by Chris Patrick Schaller and published by . This book was released on 1993 with total page 436 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Carbon-hydrogen Bond Activation and Catalytic Hydrocarbon Functionalization with Rhodium Isocyanide Complexes by : Edward T. Hessell
Download or read book Carbon-hydrogen Bond Activation and Catalytic Hydrocarbon Functionalization with Rhodium Isocyanide Complexes written by Edward T. Hessell and published by . This book was released on 1991 with total page 588 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis and Reactivity of Ruthenium and Platinum Complexes with Non-dative Heteroatomic Ligands: Studies of Carbon-hydrogen Bond Activation by :
Download or read book Synthesis and Reactivity of Ruthenium and Platinum Complexes with Non-dative Heteroatomic Ligands: Studies of Carbon-hydrogen Bond Activation written by and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Several ruthenium complexes with non-dative heteroatomic ligands were prepared and fully characterized, including TpRu(PMe3)2X (X = OH, OPh, OMe, SH; Tp = hydridotris(pyrazolyl)borate). At elevated temperatures (90 °C -- 130 °C), complexes of the type TpRu(PMe3)2X (X = OH, OPh, Me, Ph or NHPh) undergo regioselective HD exchange with deuterated arenes. In addition, for X = OH or NHPh, HD exchange occurs at hydroxo and anilido ligands, respectively. For X = OH, OPh, Me, Ph or NHPh, isotopic exchange occurs at the Tp 4-positions with only minimal deuterium incorporation at the Tp 3- or 5-positions. TpRu(PMe3)2Cl, TpRu(PMe3)2OTf (OTf = trifluoromethanesulfonate) and TpRu(PMe3)2SH do not initiate HD exchange in C6D6 after extended periods of time at elevated temperatures. Mechanistic studies indicate that the likely pathway for the HD exchange involves ligand dissociation (PMe3 or NCMe), Ru-mediated activation of an aromatic C-D bond, and deuteration of basic heteroatomic ligand (hydroxo or anilido) or Tp positions via intermolecular D+ transfer. The Ru(II) complexes TpRu(PMe3)2OR (R = H or Ph) react with excess phenylacetylene at elevated temperatures to produce the phenylacetylide complex TpRu(PMe3)2(CðCPh). Kinetic studies indicate that the reaction of TpRu(PMe3)2OH and phenylacetylene likely proceeds through a pathway that involves TpRu(PMe3)2OTf as a catalyst. The reaction of TpRu(PMe3)2OH with 1,4-cyclohexadiene at elevated temperature forms benzene and TpRu(PMe3)2H, while TpRu(PMe3)2OPh does not react with 1,4-cyclohexadiene even after 20 days at 85 °C. The paramagnetic Ru(III) complex [TpRu(PMe3)2OH][OTf] is formed upon single-electron oxidation of TpRu(PMe3)2OH with AgOTf. Reactivity studies suggest that [TpRu(PMe3)2OH][OTf] initiates reactions, including hydrogen atom abstraction, with C-H bonds that have bond dissociation energy d"82 kcalD ol. Experimentally, the O-H bond strength of the Ru(II).
Book Synopsis Transition Metal Activation and Functionalization of Carbon-hydrogen Bonds . Progress Report, December 1, 1992--November 30, 1993 by :
Download or read book Transition Metal Activation and Functionalization of Carbon-hydrogen Bonds . Progress Report, December 1, 1992--November 30, 1993 written by and published by . This book was released on 1993 with total page 3 pages. Available in PDF, EPUB and Kindle. Book excerpt: A method was developed for synthesizing a new complex for studying C-H activation, (HBPz*3)Rh(CNCH2CMe3)(PhN=C=NCH2CMe3). This complex loses the carbodiimide ligand, thereby serving as a precursor for a 16-electron Rh(I) fragment which activates (via oxidative addition) a wide range of aromatic and aliphatic C-H bonds. Mechanism of activation of benzene by this fragment was studied. Reaction of [TpR̀h(CNR)] fragment with aliphatic hydrocarbons was also studied. A study of C-H bond activation by the complex MnH3(dmpe)2 was completed. Reactions of [Ru(dmpe)2] with several small molecules were also investigated. Effects of fluorine substituents on aromatic ring on C-H activation were looked at. Studies of?2-arene coordination with [(C5Me5)Rh(PMe3)] were completed; studies of reaction of this complex with 1,3-disubstituted benzenes are in progress.
Book Synopsis Activation of Carbon-hydrogen Bonds in Alkanes and Other Organic Molecules Using Organotransition Metal Complexes by :
Download or read book Activation of Carbon-hydrogen Bonds in Alkanes and Other Organic Molecules Using Organotransition Metal Complexes written by and published by . This book was released on 1991 with total page 10 pages. Available in PDF, EPUB and Kindle. Book excerpt: We have recently begun to investigate the interaction of C-H activating iridium and rhodium complexes with functionalized organic molecules, to determine the effect of functional groups on the process, as well as to investigate the propensity of Ir and Rh to insert into C-H versus other types of X-H bonds. Recent experiments have demonstrated that xenon liquefied at -70°C and 10 atm pressure serves as an inert solvent for the C-H oxidative addition reaction. We have been able to prepare and isolate, for the first time, C-H oxidative addition products formed from high-melting solid substrates such as naphthalene, adamantane, and even cubane; the latter case represents the first observation of C-H oxidative addition at a tertiary C-H bond. Liquid xenon has also allowed us to carry out more conveniently the C-H oxidative addition reactions of low-boiling gases that are difficult to liquefy, such as methane. Recently we have also been able to carry out analogous studies in the gas phase. Under these conditions, ''naked'' rather than solvated Cp*Rh(CO) is formed, and this species reacts with cyclohexane at nearly gas-kinetic rates. Under the conditions, collision between Cp*Rh(CO) and cyclohexane is the slowest step in the overall C-H activation process. In contrast, in solution association of solvent with free Cp*Rh(CO) is so rapid that the step involving C-H bond cleavage in the coordinated alkane complex becomes rate-determining. 3 refs., 5 figs.
Book Synopsis Synthetic and Mechanistic Studies of Carbon-hydrogen Bond Activation by Iridium(III) Complexes and Development of a Transition Metal Catalyzed Alkene Aziridination Reaction by : Peter James Alaimo
Download or read book Synthetic and Mechanistic Studies of Carbon-hydrogen Bond Activation by Iridium(III) Complexes and Development of a Transition Metal Catalyzed Alkene Aziridination Reaction written by Peter James Alaimo and published by . This book was released on 1999 with total page 556 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Intermolecular and Intramolecular Carbon-hydrogen Bond Activation with Pentamethylcyclopentadienyl-rhodium-phosphine Complexes by : Valerie L. Chandler
Download or read book Intermolecular and Intramolecular Carbon-hydrogen Bond Activation with Pentamethylcyclopentadienyl-rhodium-phosphine Complexes written by Valerie L. Chandler and published by . This book was released on 1989 with total page 938 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Physical Inorganic Chemistry by : Andreja Bakac
Download or read book Physical Inorganic Chemistry written by Andreja Bakac and published by John Wiley & Sons. This book was released on 2010-04-26 with total page 635 pages. Available in PDF, EPUB and Kindle. Book excerpt: This go-to text provides information and insight into physical inorganic chemistry essential to our understanding of chemical reactions on the molecular level. One of the only books in the field of inorganic physical chemistry with an emphasis on mechanisms, it features contributors at the forefront of research in their particular fields. This essential text discusses the latest developments in a number of topics currently among the most debated and researched in the world of chemistry, related to the future of solar energy, hydrogen energy, biorenewables, catalysis, environment, atmosphere, and human health.
Book Synopsis The Activation of Carbon-hydrogen Bonds by [RH (Diphos)2]0 by : John A. Sofranko
Download or read book The Activation of Carbon-hydrogen Bonds by [RH (Diphos)2]0 written by John A. Sofranko and published by . This book was released on 1980 with total page 180 pages. Available in PDF, EPUB and Kindle. Book excerpt:
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