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Book Structural Studies of Terdentate Nitrogen Donor Ligands and Their Metal Complexes

Download or read book Structural Studies of Terdentate Nitrogen Donor Ligands and Their Metal Complexes written by Sanja Radojevic and published by . This book was released on 2001 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Synthesis and Structural Studies of Rhodium  III  Complexes of Nitrogen Donor Ligands

Download or read book Synthesis and Structural Studies of Rhodium III Complexes of Nitrogen Donor Ligands written by Tonja (Tonja Kay) Lynde-Kernell and published by . This book was released on 1986 with total page 312 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Nitrogen Donor Ligands in the Coordination Chemistry of the Rare Earth and Alkaline Earth Metals

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 Metal Complexes of Tridentate Nitrogen Donor Ligands

Download or read book Metal Complexes of Tridentate Nitrogen Donor Ligands written by Pratibha Singh and published by . This book was released on 1990 with total page 154 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Syntheses  Structures and Reactivity of the Group 6 and 7 Metal Complexes Containing Chelating Nitrogen Donor Ligands and Metal Ligand Multiple Bonds

Download or read book Syntheses Structures and Reactivity of the Group 6 and 7 Metal Complexes Containing Chelating Nitrogen Donor Ligands and Metal Ligand Multiple Bonds written by 李富華 and published by Open Dissertation Press. This book was released on 2017-01-27 with total page 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 Synthesis and Structural Studies of N  and P donor Ligands in Chromium III  Complexes

Download or read book Synthesis and Structural Studies of N and P donor Ligands in Chromium III Complexes written by Nicholas Frederick Brennan and published by . This book was released on 2013 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The fundamental knowledge of Cr(III) chemistry has been enhanced via detailed structural and spectroscopic studies of largely novel compounds that may potentially be active tri- and tetramerisation precursors. The compounds are based on various monodentate and bidentate nitrogen and phosphorus ligands which have been coordinated to [CrCl3 (thf) 3]. The few compounds that have been synthesised previously have in this study been made via novel synthetic routes and incorporate a combination of new and more detailed analysis than was carried out previously. The eight structures determined, in addition to offering novel crystallographic data, also provided insights into the synthetic pathways leading to compound formation. The isolation of monomeric structures suggests direct ligand substitution, while the cationic-anionic structures suggest the presence of dimeric intermediates which have been cleaved asymmetrically. Infrared and Raman spectra of these structures were able to add weight to these pathway proposals and, by means of vibrational comparisons, assisted in the general band assignments of the compounds' spectra where structures were not available. Vibrational shifts relative to the free ligands, as well as metal ligand vibrations in the far infrared region, were also of significant value in terms of ligand coordination and geometry. Closely associated with the infrared and Raman spectra analysis was the generation of theoretical spectra using Density Functional Theory calculations. The excellent agreement between the calculated and experimental spectra confirmed the vibrational assignments. Also generated by computational means were the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of the compounds which indicated the sites of potential nucleophilic and electrophilic attack. 1H NMR spectroscopy is a technique normally avoided when studying paramagnetic materials. However, by employing a largely novel approach, information pertaining to both ligand coordination and reaction times was obtained. FAB-MS assisted in the confirmation that the single crystal determinations did indeed reflect the composition of the bulk precipitated samples. It also provided additional structural information through the identification of fragmentation patterns which could not be gained by techniques such as elemental analysis.

Book Physico Chemical Studies of Metal Complexes with N and S Donor Ligands

Download or read book Physico Chemical Studies of Metal Complexes with N and S Donor Ligands written by Ahmad Husain and published by LAP Lambert Academic Publishing. This book was released on 2011-03 with total page 168 pages. Available in PDF, EPUB and Kindle. Book excerpt: This work describes the physico-chemical studies of metal complexes with N and S donor ligands. Emphasis has been given to the synthesis and characterization of polyazamacrocycles and dithiocarbamato complexes of transition metal ions and Sn(IV). They have been characterized by FT-IR, NMR (1H, 13C and 119Sn), mass spectrometry and X-ray crystallography. The synthesis of 14-membered hexaaza macrocyclic complexes of the type [CuL]X2, [CuL1]X2, [CuL(N3)(ClO4).3/2O]n, [CuL(N3)2] and [CuL1(N3)(ClO4)]n was reported. The effect of anions on the gross geometry and chemical properties of the Cu(II) ion have been studied. The crystal structure of [Ni(L)][CoCl4] clearly establishes the cationic-anionic interaction. Rare C H---Ni anagostic interactions, generally exhibited by d8 complexes also observed. The interaction of potassium bis(2,2-dithiopiperazinato-2,2-diaminodiethylamine (K2L) with R2SnCl2 leading to the formation of bimetallic complexes of the type R4Sn2L2 have been reported. The synthesis of a mononuclear precursor complex, [(CH3)2Sn(tpdtc)] and several heterobimetallic derivatives of the type, [(CH3)2Sn(tpdtc)]MCl2 have also been reported."

Book Synthesis  Characterization  and Structural Studies of the Metal Complexes with Ligands Derived from Triazacycloalkanes and Related Compounds

Download or read book Synthesis Characterization and Structural Studies of the Metal Complexes with Ligands Derived from Triazacycloalkanes and Related Compounds written by Delong Zhang and published by . This book was released on 1994 with total page 606 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Transition Metal Dinitrogen Complexes

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 Structural and Mechanistic Studies of Some Transition metal Complexes Containing Various Phosphorus and Carbon Donor Ligands

Download or read book Structural and Mechanistic Studies of Some Transition metal Complexes Containing Various Phosphorus and Carbon Donor Ligands written by Jonathan Michael Rosalky and published by . This book was released on 1975 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Metal Complexes with Non innocent N donor Ligands

Download or read book Metal Complexes with Non innocent N donor Ligands written by Marat M. Khusniyarov and published by . This book was released on 2006 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Conducting Metallopolymers with Tridentate Ligands and Coordination Chemistry with Corresponding Model Compounds

Download or read book Conducting Metallopolymers with Tridentate Ligands and Coordination Chemistry with Corresponding Model Compounds written by Şeyma Keskin and published by . This book was released on 2013 with total page 380 pages. Available in PDF, EPUB and Kindle. Book excerpt: Conducting polymers that contain metals are remarkable materials, because they have the properties of both organic backbones and metals. Depending on the position of the metal relative to the conjugated backbone, i.e. attached to or directly in the backbone, these two can couple resulting in advancement of the functionality and therefore potential applications of these types of materials. Complexes of tridentate ligands with donor atoms such as phosphorus, nitrogen, and sulfur also have a wide variety of applications. In addition, complexes of tridentate ligands have advantages of stability and control of electron density by variation of donor atoms. Therefore, conjugated polymers with tridentate ligand units will have promise for various applications and advantages in their designs. Complexes of PNP ligand with molybdenum and carbonyl ancillary ligands were synthesized and characterized. Isomerization and conversion reactions between them were investigated as well as the coordination modes. Many types of PNP ligands have been studied in the literature because the hemilabile property of the nitrogen atom promotes some catalytic reactions and gives different coordination geometries. Conducting polymers can be used as redox-active ligands and they can be used to control electron density on the metal attached to them. Synthesis and characterization of a novel polymerizable ligand 3,5-bis-EDOT-N,N-bis[2-diphenylphosphinoethyl]aniline was achieved. Related molybdenum complexes with ancillary ligands as carbonyls were also synthesized and characterized. Monomer complexes and the free ligand were electropolymerized and studied. Tris(bipyridine)ruthenium(II) chloride and analogous complexes have been studied extensively in the literature due to their luminescent and photochemical properties, and excited state lifetimes. Conducting polymers with similar ruthenium groups have been investigated for various applications. Synthesis of four ruthenium complexes with the polymerizable ligand 2,6-Bis[4-[2-(3,4-diethylenedioxy)thiophene]pyrazol-1-yl]pyridine and four different bidentate ligands were reproduced; electropolymerizations of the complexes were achieved; electrochemical, UV-Vis and luminescence studies were performed and discussed. Various complexes of copper, silver, platinum, and palladium with nitrogen and phosphorus donors have been reported for their luminescence behavior as well as their interesting structures. Model complexes of these metals with N,N-bis[2-(diphenylphosphino)ethyl]phenyl-amine (a PNP ligand) have been synthesized and characterized. Absorption and luminescence behaviors as well as the coordination modes were investigated.

Book Metal Ligand Interactions

    Book Details:
  • Author : N. Russo
  • Publisher : Springer Science & Business Media
  • Release : 2012-12-06
  • ISBN : 9400901550
  • Pages : 557 pages

Download or read book Metal Ligand Interactions written by N. Russo and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 557 pages. Available in PDF, EPUB and Kindle. Book excerpt: Metal-Ligand Interactions - Structure and Reactivity emphasizes the experimental determination of structure and dynamics, supported by the theoretical and computational approaches needed to establish the concepts and guide the experiments. Leading experts present masterly surveys of: clusters, inorganic complexes, surfaces, catalysis, ab initio theory, density functional theory,semiempirical methods, and dynamics. Besides the presentations of the fields of study themselves, the papers also bring out those aspects that impinge on, or could benefit from, progress in other disciplines. Refined in the fire of an interactive and stimulating conference, the papers presented here represent the state of the art of current research.