Nitrogen Donor Ligands In The Coordination Chemistry Of The Rare Earth And Alkaline Earth Metals
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Nitrogen Donor Ligands In The Coordination Chemistry Of The Rare Earth And Alkaline Earth Metals
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Author : Jelena Jenter
language : en
Publisher: Cuvillier Verlag
Release Date : 2010-05-27
Nitrogen Donor Ligands In The Coordination Chemistry Of The Rare Earth And Alkaline Earth Metals written by Jelena Jenter and has been published by Cuvillier Verlag this book supported file pdf, txt, epub, kindle and other format this book has been release on 2010-05-27 with Science categories.
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.
Bis Phosphinimino Methanides As Ligands In Rare Earth Heavy Alkaline Earth And Coinage Metal Chemistry
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Author : Tarun Kanti Panda
language : en
Publisher: Cuvillier Verlag
Release Date : 2005
Bis Phosphinimino Methanides As Ligands In Rare Earth Heavy Alkaline Earth And Coinage Metal Chemistry written by Tarun Kanti Panda and has been published by Cuvillier Verlag this book supported file pdf, txt, epub, kindle and other format this book has been release on 2005 with categories.
Molecular Catalysis Of Rare Earth Elements
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Author : Peter W. Roesky
language : en
Publisher: Springer Science & Business Media
Release Date : 2010-07-13
Molecular Catalysis Of Rare Earth Elements written by Peter W. Roesky and has been published by Springer Science & Business Media this book supported file pdf, txt, epub, kindle and other format this book has been release on 2010-07-13 with Science categories.
There is an increasing need to find cost-effective and environmentally sound methods of converting natural resources into fuels, chemicals and energy; catalysts are pivotal to such processes. Catalysis highlights major developments in this area. Coverage of this Specialist Periodical Report includes all major areas of heterogeneous catalysis. In each volume, specific areas of current interest are reviewed. Examples of topics include experimental methods, acid/base catalysis, materials synthesis, environmental catalysis, and syngas conversion.
Comprehensive Inorganic Chemistry Ii
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Author :
language : en
Publisher: Newnes
Release Date : 2013-07-23
Comprehensive Inorganic Chemistry Ii written by and has been published by Newnes this book supported file pdf, txt, epub, kindle and other format this book has been release on 2013-07-23 with Science categories.
Comprehensive Inorganic Chemistry II, Nine Volume Set reviews and examines topics of relevance to today’s inorganic chemists. Covering more interdisciplinary and high impact areas, Comprehensive Inorganic Chemistry II includes biological inorganic chemistry, solid state chemistry, materials chemistry, and nanoscience. The work is designed to follow on, with a different viewpoint and format, from our 1973 work, Comprehensive Inorganic Chemistry, edited by Bailar, Emeléus, Nyholm, and Trotman-Dickenson, which has received over 2,000 citations. The new work will also complement other recent Elsevier works in this area, Comprehensive Coordination Chemistry and Comprehensive Organometallic Chemistry, to form a trio of works covering the whole of modern inorganic chemistry. Chapters are designed to provide a valuable, long-standing scientific resource for both advanced students new to an area and researchers who need further background or answers to a particular problem on the elements, their compounds, or applications. Chapters are written by teams of leading experts, under the guidance of the Volume Editors and the Editors-in-Chief. The articles are written at a level that allows undergraduate students to understand the material, while providing active researchers with a ready reference resource for information in the field. The chapters will not provide basic data on the elements, which is available from many sources (and the original work), but instead concentrate on applications of the elements and their compounds. Provides a comprehensive review which serves to put many advances in perspective and allows the reader to make connections to related fields, such as: biological inorganic chemistry, materials chemistry, solid state chemistry and nanoscience Inorganic chemistry is rapidly developing, which brings about the need for a reference resource such as this that summarise recent developments and simultaneously provide background information Forms the new definitive source for researchers interested in elements and their applications; completely replacing the highly cited first edition, which published in 1973
Synthesis And Applications In Chemistry And Materials In 4 Volumes
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Author : Armando J L Pombeiro
language : en
Publisher: World Scientific
Release Date : 2024-01-16
Synthesis And Applications In Chemistry And Materials In 4 Volumes written by Armando J L Pombeiro and has been published by World Scientific this book supported file pdf, txt, epub, kindle and other format this book has been release on 2024-01-16 with Science categories.
Chemistry and Material Sciences naturally depend greatly on Synthesis as the initial stage for the existence of compounds and materials with desired behaviors, within the overall streamline of Design/Synthesis — Properties — Application/Function, and their relations. Such a general approach is of a too wide scope to be properly treated in a single set of publications, but this one on 'Synthesis and Applications in Chemistry and Materials' restricts itself by aiming to show the strength and international character of the current research in synthetic chemistry that is being developed in Portugal or abroad by teams that cooperate with this country. Hence, it gathers representative contributions of main Portuguese research groups and foreign collaborating ones. Nevertheless, the topic should be understood in a wide sense, being open to types of studies with significance on sustainable synthesis and applications in chemistry, materials and/or related sciences.
Rare Earth Elements Fluorides Flouride Oxides And The Related Alkali Double Salts
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Author :
language : en
Publisher:
Release Date : 1994
Rare Earth Elements Fluorides Flouride Oxides And The Related Alkali Double Salts written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1994 with Chemistry, Inorganic categories.
Handbook On The Physics And Chemistry Of Rare Earths
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Author :
language : en
Publisher: Elsevier
Release Date : 2017-07-18
Handbook On The Physics And Chemistry Of Rare Earths written by and has been published by Elsevier this book supported file pdf, txt, epub, kindle and other format this book has been release on 2017-07-18 with Science categories.
Handbook on the Physics and Chemistry of Rare Earths: Including Actinides, Volume 51, is a continuous series of books covering all aspects of rare earth science, including chemistry, life sciences, materials science and physics. This latest release includes chapters on the Effect of Pressure on the Interplay Between Orbital and Magnetic Ordering, Kondo Effect, Valence Fluctuation, and Superconductivity in Rare-Earth Compounds and a section on Rare-Earth: Doped Waveguide Amplifiers and Lasers. The book's main emphasis is on rare earth elements [Sc, Y, and the lanthanides (La through Lu], but whenever relevant, information is also included on the closely related actinide elements. Individual chapters in the ongoing series consist of comprehensive, broad, up-to-date, critical reviews written by highly experienced, invited experts. The series, which was started in 1978 by Professor Karl A. Gschneidner Jr., combines, and integrates, both the fundamentals and applications of these elements with two published volumes each year. Presents up-to-date overviews and new developments in the field of rare earths, covering both their physics and chemistry Contains Individual chapters that are comprehensive and broad, with critical reviews Provides contributions from highly experienced, invited experts
Proceedings Of The Estonian Academy Of Sciences Physics And Mathematics
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Author :
language : en
Publisher:
Release Date : 2003-09
Proceedings Of The Estonian Academy Of Sciences Physics And Mathematics written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2003-09 with categories.
Journal Of The Indian Chemical Society
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Author : Indian Chemical Society
language : en
Publisher:
Release Date : 1992
Journal Of The Indian Chemical Society written by Indian Chemical Society and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1992 with Chemistry categories.
Physical Inorganic Chemistry
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Author : S. F. A. Kettle
language : en
Publisher: Springer
Release Date : 2013-11-11
Physical Inorganic Chemistry written by S. F. A. Kettle and has been published by Springer this book supported file pdf, txt, epub, kindle and other format this book has been release on 2013-11-11 with Science categories.
GEORGE CHRISTOU Indiana University, Bloomington I am no doubt representative of a large number of current inorganic chemists in having obtained my undergraduate and postgraduate degrees in the 1970s. It was during this period that I began my continuing love affair with this subject, and the fact that it happened while I was a student in an organic laboratory is beside the point. I was always enchanted by the more physical aspects of inorganic chemistry; while being captivated from an early stage by the synthetic side, and the measure of creation with a small c that it entails, I nevertheless found the application of various theoretical, spectroscopic and physicochemical techniques to inorganic compounds to be fascinating, stimulating, educational and downright exciting. The various bonding theories, for example, and their use to explain or interpret spectroscopic observations were more or less universally accepted as belonging within the realm of inorganic chemistry, and textbooks of the day had whole sections on bonding theories, magnetism, kinetics, electron-transfer mechanisms and so on. However, things changed, and subsequent inorganic chemistry teaching texts tended to emphasize the more synthetic and descriptive side of the field. There are a number of reasons for this, and they no doubt include the rise of diamagnetic organometallic chemistry as the dominant subdiscipline within inorganic chemistry and its relative narrowness vis-d-vis physical methods required for its prosecution.
