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Non Cp Metal Complexes Supported By Nitrogen Donor Ligands Precursors For The Synthesis Of New Metal
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Book Synopsis Non-Cp Metal Complexes Supported by Nitrogen Donor Ligands: Precursors for the Synthesis of New Metal by : Haijun Hao
Download or read book Non-Cp Metal Complexes Supported by Nitrogen Donor Ligands: Precursors for the Synthesis of New Metal written by Haijun Hao and published by . This book was released on 2001 with total page 82 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Non-Cp Metal Complexes Supported by Nitrogen Donor Ligands by :
Download or read book Non-Cp Metal Complexes Supported by Nitrogen Donor Ligands written by and published by . This book was released on 2001 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, Characterization, and Reactivity of Transition Metal Complexes Supported by Heteropolydentate Ligation by : Adam Ruddy
Download or read book Synthesis, Characterization, and Reactivity of Transition Metal Complexes Supported by Heteropolydentate Ligation written by Adam Ruddy and published by . This book was released on 2014 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Direct Synthesis of Metal Complexes by : B.I. Kharisov
Download or read book Direct Synthesis of Metal Complexes written by B.I. Kharisov and published by Elsevier. This book was released on 2018-04-19 with total page 470 pages. Available in PDF, EPUB and Kindle. Book excerpt: Direct Synthesis of Metal Complexes provides in-depth coverage of the direct synthesis of coordination and organometallic compounds. The work is primarily organized by methods, but also covers highly relevant complexes, such as metal-polymer coordination compounds. This updated reference discusses recent developments in cryosynthesis, electrosynthesis, and tribosynthesis (popular as it doesn’t require organic solvents), with special attention paid to ‘greener’ methodologies and approaches. Additionally, the book describes physical methods of zero-valent metal interaction with organic matter, including sputtering, ultrasonic treatment and synthesis in ionic liquids. The book presents completely new content as a follow-up to the 1999 Elsevier Science publication Direct Synthesis of Coordination and Organometallic Compounds that was edited by Dr. Garnovskii and Dr. Kharisov. Covers current methods and techniques of metal interactions with organic media leading to metal chelates, adducts, di- and polymetallic complexes, metal-containing macrocycles, supported coordination compounds (i.e., metal complexes on carbon nanotubes), and more Describes reactivities of distinct forms of elemental metals (powders, sheets, nanoparticles (including a host of less-common metal nanostructures) with organic phase (liquid, solid and gaseous) and water Includes experimental procedures, with examples of direct synthesis, at the end of each chapter
Book Synopsis Nitrogen Donor Ligands in the Coordination Chemistry of the Rare Earth and Alkaline Earth Metals by : Jelena Jenter
Download or read book Nitrogen Donor Ligands in the Coordination Chemistry of the Rare Earth and Alkaline Earth Metals written by Jelena Jenter and published by Cuvillier Verlag. This book was released on 2010-05-27 with total page 134 pages. Available in PDF, EPUB and Kindle. Book excerpt: Bis(phosphinimino)methanide rare earth metal bisborohydrides, as illustrated in Scheme I, were successfully synthesized by salt metathesis reactions of [K{CH(PPh2NSiMe3)2}] with [Ln(BH4)3(THF)n] (Ln = Sc (n = 2); Ln = La, Nd, Lu (n = 3)) or in the case of yttrium by the reaction of [{(Me3SiNPPh2)2CH}YCl2]2 with NaBH4. Interestingly, the BH4- anions are ?3-coordinated in the solid state structures of 3, 4, 6 and 7, while for the scandium complex 5 two different conformational polymorphs were identified, in which either both BH4- groups are ?3-coordinated or one BH4- anion shows an ?2-coordination mode. Furthermore, complexes 3, 6 and 7 showed high activities in the ring-opening polymerization (ROP) of e-caprolactone (CL). At 0 °C, the molar mass distribution reached the narrowest values ever obtained for the ROP of CL initiated by a rare earth metal borohydride species. In collaboration with N. Meyer, rare earth metal chlorides and borohydrides of the 2,5-bis{N-(2,6-diisopropylphenyl)iminomethyl}pyrrolyl ligand were synthesized, as shown in Scheme II. The reaction of [(DIP2pyr)K] (10) with anhydrous neodymium trichloride afforded [(DIP2pyr)NdCl2(THF)]2 (12) which is dimeric in the solid state. Excitingly, the reaction of [(DIP2pyr)K] (10) with [Ln(BH4)3(THF)n] (Ln = Sc (n = 2); Ln = La, Nd, Lu (n = 3)) depends on the ionic radii of the center metals. For the larger rare earth metals lanthanum and neodymium, the expected products [(DIP2pyr)Ln(BH4)2(THF)2] (Ln = La (13), Nd (14)) were obtained; while for the smaller rare earth metals scandium and lutetium, an unusual redox reaction of a BH4- anion with one of the Schiff-base functions of the ligand was observed and the products [{DIP2pyr*-BH3}Ln(BH4)(THF)2] (Ln = Sc (15), Lu (16)) were formed (Scheme II). Moreover, the two neodymium containing complexes 12 and 14 were investigated as Ziegler-Natta catalysts for the polymerization of 1,3-butadiene to form poly-cis-1,4-butadiene, by using various cocatalyst mixtures. Very high activities and good selectivities were observed for 12. The 2,5-bis{N-(2,6-diisopropylphenyl)iminomethyl}pyrrolyl ligand was successfully introduced into the coordination chemistry of the divalent lanthanides and the alkaline earth metals. As shown in Scheme III, salt metathesis reactions of [(DIP2pyr)K] (10) with either anhydrous lanthanide diiodides or alkaline earth metal diiodides afforded the corresponding heteroleptic iodo complexes [(DIP2pyr)LnI(THF)3] (Ln = Sm (19), Eu (20), Yb (21)) or [(DIP2pyr)MI(THF)n] (M = Ca (24), Sr (22) (n = 3); Ba (23) (n = 4)). Surprisingly, all complexes 19-24 are monomeric in the solid state, independently from the ionic radii of their center metals. Instead of forming dimers, the coordination sphere of each metal center is satisfied by additionally coordinated THF molecules, which is a very rare structural motif in the chemistry of the larger divalent lanthanides and alkaline earth metals. While the (DIP2pyr)- ligands in 19-23 are ?3-coordinated in the solid state, for the calcium complex 24 an ?2-coordination mode was observed (Scheme III). Interestingly, the calcium complex 24 and the analogous ytterbium compound 21 show different structures in the solid state. In order to obtain catalytically active species, [(DIP2pyr)M{N(SiMe3)2}(THF)2] (M = Ca (25), Sr (26)) were prepared by the reaction of [(DIP2pyr)MI(THF)3] (M = Ca (24), Sr (22)) with [K{N(SiMe3)2}] (Scheme IV). Compounds 25 and 26 were investigated for the intramolecular hydroamination of aminoalkenes and one aminoalkyne. Unfortunately, both catalysts exhibit a limited reaction scope, caused by the formation of undesired side products by alkene isomerization and imine-enamine tautomerism. However, both compounds are active catalysts and show high yields and short reaction times. The highest activities were observed for the calcium complex 25 and can be compared to the results obtained with the ß-diketiminato calcium amide [{(DIPNC(Me))2CH}Ca{N(SiMe3)2}(THF)] as a catalyst. Finally, imidazolin-2-imide and cyclopentadienyl-imidazolin-2-imine rare earth metal alkyl complexes, synthesized by M. Tamm et al., were investigated for the intramolecular hydroamination of non-activated aminoalkenes and one aminoalkyne. Both compounds showed high selectivities and activities, and although they cannot compete with the metallocene analogues, the imidazolin-2-imide complexes are new and interesting examples for catalytically active post-metallocenes.
Book Synopsis Synthesis of Group 9 and 10 Metal Complexes Supported by Chelating Nitrogen-based Ligands and Mechanistic Studies of Their Role in Catalytic Transformations by : Jennifer Lauren McBee
Download or read book Synthesis of Group 9 and 10 Metal Complexes Supported by Chelating Nitrogen-based Ligands and Mechanistic Studies of Their Role in Catalytic Transformations written by Jennifer Lauren McBee and published by . This book was released on 2009 with total page 840 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis of Reactive Metal Complexes Supported by 1,1'-disubstituted Ferrocene Ligands by : Jonathan Lee Brosmer
Download or read book Synthesis of Reactive Metal Complexes Supported by 1,1'-disubstituted Ferrocene Ligands written by Jonathan Lee Brosmer and published by . This book was released on 2017 with total page 155 pages. Available in PDF, EPUB and Kindle. Book excerpt: Reliable transformation of low-cost rare-earth metal oxides to organometallic rare-earth metal complexes is a prerequisite for the advancement of non-aqueous rare-earth metal chemistry. We have recently developed an in situ method to prepare rare-earth alkyl and halide precursors supported by a diamidoferrocene NNfc, 1,1'-fc(NSiMe2Bu)2, as an ancillary ligand. We extended the scope of this method to other lanthanide ions including those that are redox active, such as cerium, praseodymium, samarium, terbium, thulium, and ytterbium. Specifically, samarium trisbenzyl could be generated in situ and then converted to the corresponding samarium benzyl or iodide complexes in good yield. However, it was found that ytterbium trisbenzyl could not be formed cleanly and the consequent conversion to ytterbium iodide complex was low yielding. By adapting an alternative route, the desired ytterbium chloride precursor could be obtained in good yield and purity. The synthesis and characterization of two yttrium alkyl complexes supported by a bisphosphinimine ferrocene ligand, NPfc (1,1 -di(2,4-di-tert-butyl-6-diphenylphosphiniminophenoxy)ferrocene), were accomplished. Although (NPfc)Y(CH2Ph) and (NPfc)Y(CH2SiMe3) could be structurally characterized, these compounds are thermally sensitive and decompose at ambient temperature within hours. Their characterization was accomplished by NMR spectroscopy, electrochemical measurements, and elemental analysis. Reactivity studies were also carried out; however, the lack of prolonged thermal stability at ambient temperature of these molecules led to decomposition before a clean transformation to reaction products could be observed. The synthesis and characterization of Ln-C4Ph4-K, [(NNTBS)Ln( 2-C4Ph4)][K(THF)x] (Ln = Sc, Y, Lu), rare-earth metal complexes supported by a ferrocene diamide ligand, NNTBS (NNTBS = fc(NSitBuMe2)2, fc = 1,1 -ferrocenediyl), were accomplished. The preparation of the half-sandwich compounds, Ln-naph-K, [(NNTBS)Ln( -C10H8)][K(THF)2] (Ln = Sc, Y, Lu, La), was necessary in order to obtain high yields of rare-earth metallacyclopentadienes. Unlike Y and Lu, La did not show the same reactivity toward PhCCPh. The characterization of the new metal complexes was accomplished by NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction.
Book Synopsis Metallocenes in Regio- and Stereoselective Synthesis by : Marko Hapke
Download or read book Metallocenes in Regio- and Stereoselective Synthesis written by Marko Hapke and published by Springer. This book was released on 2024-06-20 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book presents the latest synthetic protocols for the assembly of functionalized Cp ligands and their transition metal complexes. Cyclopentadienyl (Cp) complexes of transition metals belong to the most important classes of transition metal complexes with tightly bound ligands in the coordination sphere since their discovery in the middle of the last century. Even though they have been known for a long time, this field constantly evolves to deliver novel modified Cp ligands and complexes and to blossom into new fields of application. Beside the synthesis of ligands and metal complexes this book concentrates on novel and prospering fields of their application in organic synthesis. In this respect the Cp complexes have been applied to induce and catalyze various significant chemical transformations such as new C-C bond formation involving unsaturated substrates (e.g. cyclotrimerizations, cycloadditions, carbometallations, etc.), C-H bond and C-C bond activations followed by subsequent reactions (e.g. arylation, alkenylations, annulations, etc.), as well as many other processes. This volume also covers the recent development and application of chiral Cp complexes in enantioselective synthesis.
Book Synopsis The Synthesis and Structural Characterization of Main Group and Transition Metal Complexes Supported by Nitrogen Based Ligands by :
Download or read book The Synthesis and Structural Characterization of Main Group and Transition Metal Complexes Supported by Nitrogen Based Ligands written by and published by . This book was released on 2001 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Nitrogen based monodentate and bidentate chelating ligands have captured a significant interest due to their ability to coordinate to a wide variety of elements. The â-diketimine, â-ketoiminato, formamidine, pyridineselenolate, and pyrazinecarboxamide ligands have all been employed in this study to further investigate the coordination preferences among main group and transition metals. Steric and electronic properties of these ligands can easily be altered by manipulating the substituents attached, thus leading to predictable structures with potential for many useful and significant applications. Investigations have shown that temperature, solvent, and metal halide employed are all key factors in the reaction outcomes. All of the complexes obtained throughout these studies have been characterized by X-ray crystallography along with other spectroscopic techniques, including NMR, IR, UV/Vis, and M/S. â-diketiminato ligands, [{N(R)C(Me)}2C(H)] where R = Dipp, Mes, commonly referred to as nacnac, have played an important role in the synthesis of novel pnictogenium complexes. Results show that through manipulation of the halide precursor, reaction stoichiometry, and the R substituent on the nacnac both N, N'- and N, C'-metal chelated complexes can be achieved. Additionally, â-ketiminato ligands, [RN(H)(C(Me))2C(Me)=O] where R = Dipp, and [RN(H)C(Me)CHC(Me)=O] where R = C2H4NEt2, have been studied. Both ligands were investigated with a range of d and p block metal halides and alkyls in order to compare and contrast the bulky, flexible, and even multi-dentate nature of each ligand. The preferred metal geometry remains constant for products with either ligand, but the steric protection offered by the individual ligands governs the nuclearity of the products, ranging from tetrameric cages to simple adducts. The formamidinate ligand, [RN(H)C(H)NR] where R = Dipp, was employed in synthesizing several aluminum and zinc complexes. In addition to their numerous applications as cata.
Book Synopsis Main Group and Transition Metal Complexes Supported by Multidentate Tripodal Ligands that Feature Nitrogen, Oxygen and Sulfur Donors by :
Download or read book Main Group and Transition Metal Complexes Supported by Multidentate Tripodal Ligands that Feature Nitrogen, Oxygen and Sulfur Donors written by and published by . This book was released on 2013 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter 5 describes two multidentate, L3X type ligands, which feature [CN3] and [CNO2] donors, namely tris(2 pyridylseleno)methane, [Tpsem]H, and bis(2-pyridonyl)(pyridin-2-yloxy)methane, [O-poBpom]H. They have been synthesized, characterized, and employed in the synthesis of zinc and cadmium complexes. Chapter 6 describes the synthesis and structural characterization of a new [Tp] ligand featuring an allyl substituent on the central boron atom, namely [allylTpBut]Li is reported. The compound reacts steadily with CH3CH2SH under 350 nm UV light via a thiol-ene click reaction. The resulting [CH3CH2S(CH2)3TpBut]Li complex can further react with metal halide. For example, the reaction of [CH3CH2S(CH2)3TpBut]Li with ZnI2 produced [CH3CH2S(CH2)3TpBut]ZnI at room temperature. This study provides a simple model on the immobilization of [Tp] metal complexes to the polymer chains with -SH terminals.
Book Synopsis SYNTHESES STRUCTURES & REACTIV by : 李富華
Download or read book SYNTHESES STRUCTURES & REACTIV written by 李富華 and published by Open Dissertation Press. This book was released on 2017-01-27 with total page 244 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Syntheses, Structures and Reactivity of the Group 6 and 7 Metal Complexes Containing Chelating Nitrogen Donor Ligands and Metal-ligand Multiple Bonds" by 李富華, Fu-wa, Lee, 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. Abstract: Abstract of thesis entitled "SYNTHESES, STRUCTURES AND REACTIVITY OF THE GROUP 6 AND 7 METAL COMPLEXES CONTAINING CHELATING NITROGEN DONOR LIGANDS AND METAL-LIGAND MULTIPLE BONDS" submitted by Lee Fu Wa for the degree of Doctor of Philosophy at the University of Hong Kong in September, 1997. ____________________________________________________________________ [Cr(CRMe )Cl ] (CRMe =meso-2,3,7,11,12-pentamethyl-3,7,11,17- 3 2 3 2+ tetraazabicyclo[11.3.1]-heptadeca-1(17),13,15-triene), [Cr(CRMe )Cl(H O)], 3 2 2+ + [Cr(CRMe )Cl(CH CN)] and [Cr(CRMe )(N )(OH)] are prepared. Upon addition 3 3 3 3 2+ 2+ of PhI=O to solutions of [Cr(CRMe )Cl(CH CN)] and [Cr(CRMe )Cl(H O)] 3 3 3 2 respectively in CH CN, the UV-visible absorption spectra of the two mixtures show similar isosbestic spectral changes attributed to the formation of V 2+ [Cr (CRMe )Cl(O)] . Addition of PhP causes the immediate recovery of 3 3 2+ [Cr(CRMe )Cl(CH CN)] as the isosbestic changes are reversed. Irradiation of 3 3 [Cr(CRMe )(N )(OH)] in acetonitrile with UV-visible light gives an azide-free 3 3 product, the FAB-MS of which shows a molecular ion peak indicative of V + + ([Cr (CRMe )(N)]ClO ). The UV-visible spectra of [Cr(CRMe )Cl ], 3 4 3 2 2+ 2+ [Cr(CRMe )Cl(H O)] and [Cr(CRMe )Cl(CH CN)] measured in water are 3 2 3 3 3+ similar to that of [Cr(CRMe )(H O) ] . Results from the conductivity measurement 3 2 2 + 2+ show that in water, [Cr(CRMe )Cl ], [Cr(CRMe )Cl(H O)] and 3 2 3 2 2+ [Cr(CRMe )Cl(CH CN)] behave as 3:1 electrolytes. The species which exists in 3 3 3+ water is likely to be the di-aquo complex [Cr(CRMe )(H O) ] . 3 2 2 2+ 2+ [Cr(CRMe )Cl(H O)] and [Cr(CRMe )Cl(CH CN)] are both found to give a 3 2 3 3 reversible oxidation couple at +1.11 V vs. SCE in aqueous solutions at pH=1 which is assigned to Cr(III)/(IV). iii t + The bis(imido) complexes [(TACN)M(N Bu) Cl] (M=Cr, Mo; TACN=1,4,7-triazacyclononane) and their 1,4,7-trimethyl derivatives are prepared, the crystal structures of which reveal the trans influence of the imido group. These 0 +/0 d species display a quasi-reversible couple at potentials 0.86 - 1.20 V vs. Cp Fe in acetonitrile assignable to a imido ligand-centred oxidation. (Me TACN)Mo(CO), 1,4,7-Tri((S)-2-methylbutyl)-1,4,7-triazacyclononane 3 3 * * * (L ) and L Mo(CO) are synthesized. (Me TACN)Mo(CO) and L Mo(CO) show 3 3 3 3 +/0 reversible oxidation couples at -0.26 V and -0.24 V vs. Cp Fe in CH CN 2 3 I/0 respectively which are assigned to Mo . The comparable electronic effect of * Me TACN and L in this system is therefore implied. 2+ [(Me TACN) Mn (μ-O)(μ-OCOCH ) ] is prepared and found to mediate 3 2 2 3 2 aziridination of styrene, methylstyrene, cis- and trans-stilbene, 1,1-diphenylethene and norbornene by PhI=NTs in CH Cl at 25 C. The nitrene transfer to cis- and 2 2 trans-stilbene is found to be stereoselective to exclusively give the trans-aziridine product. + + [(Me TACN)(CO) M CPh] (M=Mo, W) and [(TACN)(CO) Mo CPh] 3 2 2 are prepared. [(Me TACN)(CO) M CPh] (M=Mo, W) exhibit a reversible 3 2 +/0 reduction couple at -2.15 V vs Fe Cp and an irreversible wave at 0.77 V vs +/0 Fe Cp, which are ascribed to a reduction centred at the phenyl ring and oxidation of the terminal CO respectively. Treatment of Cl(
Book Synopsis Design and Synthesis of New Ligand Systems for Transition Metal Catalysed Carbon-carbon Cross-coupling, Hydrogenation and Hydrosilation by : Daniel Carleton
Download or read book Design and Synthesis of New Ligand Systems for Transition Metal Catalysed Carbon-carbon Cross-coupling, Hydrogenation and Hydrosilation written by Daniel Carleton and published by . This book was released on 2013 with total page 248 pages. Available in PDF, EPUB and Kindle. Book excerpt: An ever increasing global requirement for consumables consequently increases the demand for often non-renewable resources, resulting in the need for greater efficiencies in synthetic processes. In order to achieve this goal, the field of organometallic catalysis has been ever growing to support the ideals of cleaner and greener chemistry. In this thesis studies concerning a series of new bidentate donor ligands employing both the NHC and PYA donor groups for use in transition metal catalysis is presented. The successful synthesis of the bidentate ligand N,N'-dimethyl-N''-pyridin-4-yl nicotinamide with both a remote NHC and PYA donor groups is reported, along with the synthesis of the precursor materials 1-methyl-3-(2-oxo-2-(pyridin-2-ylamino)ethyl)-1H-imidazol-3-ium and 1-methyl-3-(2-oxo-2-(pyridin-4-ylamino)ethyl)-1H-imidazol-3-ium for the formation of other bidentate ligands incorporating the imidazolium NHC and PYA donor groups. The iridium complex IrH(L-R4)(CO)(PPh3)2 containing the new ligand L-R4 was prepared through reaction of N,N'-dimethyl-N''-pyridin-4-yl nicotinamide with Vaskas Complex. Chapter one explains the ideology behind green chemistry and our constant drive to maintain a clean and green planet. Chapter two describes the effect of donor groups on a metal centre with focus on the NHC and PYA donor groups and their advantages over previous work in this area. Chapter three describes the development of synthetic routes to the new target ligands and chapter four explains the studies involving the metal precursor substrates and ligand coordination. Chapter five contains details of the relevant experimental data. The work described in this thesis will provide an excellent starting point for those wishing to further explore the synthesis and study of bidentate NHC and PYA donor ligands in catalysis by transition metals.
Book Synopsis Metal Complexes with Non-innocent N-donor Ligands: Molecular and Electronic Structures, Reactivity, and Application by :
Download or read book Metal Complexes with Non-innocent N-donor Ligands: Molecular and Electronic Structures, Reactivity, and Application written by and published by . This book was released on 2006 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The present work comprises different aspects of coordination chemistry of non-innocent, or redox active, ligands. The most attention is given to the complexes of late transition metals as well as phthalocyanines of alkaline earth metals. The dissertation covers synthesis of complexes with non-innocent ligands and investigation of their molecular and electronic structures by set of methods including X-ray crystallography, EPR, NMR and electronic spectroscopy, electro- and magnetochemistry. Application such of complexes as catalysts for olefin polymerization or one-dimensional conducting materials is presented. I hope this work will be of interest as for synthetic chemists as well as for physical chemists having interest in application of variety of spectroscopic methods to allow deep understanding of coordination compounds with sophisticated electronic structures.
Book Synopsis Transition Metal Complexes with Multidentate Phosphorous/nitrogen Ligands. Synthesis, Characterization and Reactivity by : Sergio Santiago Rozenel
Download or read book Transition Metal Complexes with Multidentate Phosphorous/nitrogen Ligands. Synthesis, Characterization and Reactivity written by Sergio Santiago Rozenel and published by . This book was released on 2011 with total page 256 pages. Available in PDF, EPUB and Kindle. Book excerpt: Abstract Transition metal complexes with multidentate phosphorous/nitrogen ligands. Synthesis, characterization and reactivity. By Sergio Santiago Rozenel Doctor in Philosophy in Chemistry University of California, Berkeley Professor John Arnold, Chair Chapter 1: Chromium complexes supported by the multidentate monoanionic ligand [N2P2] {H[N2P2] = tBuN(H)SiMe2N(CH2CH2PiPr2)2} are presented, and the activity of these complexes towards ethylene oligomerization/polymerization is examined. The complexes [N2P2]CrCl2 (1) and [N2P2]CrCl (2) polymerized ethylene after activation with MAO. Derivatives of 1 and 2 were synthesized in order to gain insights about the active species in the ethylene oligomerization/polymerization processes. The alkyl complexes [N2P2]CrMe (3), [N2P2]CrCH2SiMe3 (4) and [N2P2]Cr(Cl)CH2SiMe3 (5), the cationic species {[N2P2]CrCl}BF4 (7), {[N2P2]CrCl}BPh4 (8) and {[N2P2]CrCH2SiMe3}BF4 (9), and the Cr(II) complex [N2P2]CrOSO2CF3 (11) were not active ethylene oligomerization/polymerization catalysts in absence of an activator. Reaction of 1 with two equivalents of MeLi led to reduction to 3. However, with one equivalent of MeLi the stable mixed alkyl-halide derivative [N2P2]Cr(Cl)Me (6) was obtained. Reaction of 2 with Red-Al® produced the hydride ([N2P2]Cr)2(ì-H)2 (10), which reacted with CO to produce the Cr(I) complex [N2P2]Cr(CO)2 (12). Reduction of 2 with KC8 in the presence of p-tolyl azide produced the dimeric cis μ-imido ([N2P2]Cr)2(ì-NC7H7)2 (13). A similar reduction in the presence of ethylene resulted in the isolation of the Cr(III) metallacyclohexane compound [N2P2]CrC4H8 (14). Chapter 2: A series of Co, Ni and Cu complexes with the ligand HN(CH2CH2PiPr2)2 (HPNP) has been isolated and their electrochemical behavior investigated by cyclic voltammetry. The nickel complexes [(HPNP¬)NiOTf]OTf and [(HPNP)NiNCCH3](BF4)2 display reversible reductions, as does the related amide derivative (NP2)NiBr. Related copper(I) and cobalt(II) derivatives were isolated and characterized. Addition of piperidine to [(HNP2)NiNCCH3](BF4)2 led to the formation of the new species [(HPNP)Ni(N(H)C(CH3)NC5H10)](BF4)2. Nucleophilic addition of piperidine to acetonitrile to produce HN=C(CH3)NC5H10 was catalyzed by [(HPNP)NiNCCH3](BF4)2. Chapter 3: A series of bimetallic ruthenium complexes [HPNPRu(N2)]2(μ-Cl)2](BF4)2 (2), [(HPNPRu(H2)Cl)2(μ-Cl)2](BF4)2 (3), [(HPNPRu)2(μ-H2NNH2)(μ-Cl)2](BF4)2 (4), [(HPNPRu)2(μ-Cl)2(μ-HNNPh)](BF4)2 (5), [HPNPRu(NH3)(ç2-N2H4)](BF4)Cl (6), [(HNP2Ru)2(μ-Cl)2(μ2-OSO2CF3)]OSO2CF3 (7), [HPNPRu]2(μ-Cl)3]BPh4 (8) and [HPNPRu]2(μ-Cl)3]BF4 (9) were isolated and characterized in the course of reactions aimed at studying the reduction of N2 and hydrazine. Complex 4 produces ammonia catalytically from hydrazine, and complex 2 generates ammonia upon reaction with Cp2Co/HLuBF4. DFT calculations support the idea that the diazene complex formed is more stable than the expected Chatt-type intermediate. Chapter 4: The reduction chemistry of cobalt complexes with the PNP ligand was explored. Reaction of (HPNP)CoCl2 (1) with n-BuLi generated the deprotonated Co(II) product (PNP)CoCl (2), and the Co(I) reduced species (HPNP)CoCl (3). The reaction of complex 2 with KC8 was investigated, where it was found that the products obtained depended upon the inert gas used to carry out the reaction: (PNP)CoN2 (4) under N2, bimetallic complex [(PNP)Co]2 (5) under Ar, and (HPNP)Co(H)3 (8) under H2. Complex 5 reacted with H2 to generate the bimetallic complex [(PNP)CoH]2 (6). With H2, H3SiPh and AgBPh4 complex 3 generated the species (HPNP)CoCl(H)2 (9), (HPNP)CoCl(H)SiH2Ph (10) and [(HPNP)CoCl]BPh4 (11) respectively. DFT calculations were performed to gain insights about the transformations observed.
Book Synopsis Transition Metal-Dinitrogen Complexes by : Yoshiaki Nishibayashi
Download or read book Transition Metal-Dinitrogen Complexes written by Yoshiaki Nishibayashi and published by John Wiley & Sons. This book was released on 2019-01-25 with total page 510 pages. Available in PDF, EPUB and Kindle. Book excerpt: A comprehensive book that explores nitrogen fixation by using transition metal-dinitrogen complexes Nitrogen fixation is one of the most prominent fields of research in chemistry. This book puts the focus on the development of catalytic ammonia formation from nitrogen gas under ambient reaction conditions that has been recently repowered by some research groups. With contributions from noted experts in the field, Transition Metal-Dinitrogen Complexes offers an important guide and comprehensive resource to the most recent research and developments on the topic of nitrogen fixation by using transition metal-dinitrogen. The book is filled with the information needed to understand the synthesis of transition metal-dinitrogen complexes and their reactivity. This important book: -Offers a resource for understanding nitrogen fixation chemistry that is essential for explosives, pharmaceuticals, dyes, and all forms of life -Includes the information needed for anyone interested in the field of nitrogen fixation by using transition metal-dinitrogen complexes -Contains state-of-the-art research on synthesis of transition metal-dinitrogen complexes and their reactivity in nitrogen fixation -Incorporates contributions from well-known specialists and experts with an editor who is an innovator in the field of dinitrogen chemistry Written for chemists and scientists with an interest in nitrogen fixation, Transition Metal-Dinitrogen Complexes is a must-have resource to the burgeoning field of nitrogen fixation by using transition metal-dinitrogen complexes.
Book Synopsis The Organometallic Chemistry of the Transition Metals by : Robert H. Crabtree
Download or read book The Organometallic Chemistry of the Transition Metals written by Robert H. Crabtree and published by John Wiley & Sons. This book was released on 2005-06-14 with total page 600 pages. Available in PDF, EPUB and Kindle. Book excerpt: Fully updated and expanded to reflect recent advances, this Fourth Edition of the classic text provides students and professional chemists with an excellent introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications.
Book Synopsis Transition Metal Complexes of Novel Nitrogen Donor Ligands by : David George Lonnon
Download or read book Transition Metal Complexes of Novel Nitrogen Donor Ligands written by David George Lonnon and published by . This book was released on 2005 with total page 514 pages. Available in PDF, EPUB and Kindle. Book excerpt:
