N-heterocyclic Silyl and Silylene Metal Complexes Within a PSIP Framework PDF Download
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Author: Amy Marie Jehl
Publisher:
ISBN: 9781085729345
Category : Carbon dioxide
Languages : en
Pages : 237
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Book Description
N-heterocyclic carbenes (NHC) are strong Lewis bases that have demonstrated broad utility as ligands for transition metal (TM) catalysts. Silicon analogues, N-heterocyclic silylenes (NHSi), are comparatively less well studied. The decreased [Pi]-[pi] overlap between the Si 3p orbital and adjacent nitrogen lone pairs creates a more accessible vacant orbital on Si, resulting in increased ambiphilic character. When bound to a transition metal, this empty orbital presents an opportunity to cooperatively bind and activate substrate molecules. To increase the stability of a potential metal-silylene complex we targeted the diphosphine ligand precursor 1,2-bis(R2PCH2NCH2)C6H4 (R = alkyl or aryl), first reported by Yamashita and Nozaki in the construction of a boron-anchored pincer. Reported here are (PCy)2Si pincer ligands and their TM-silylene complexes for small molecule activation.
Author: Amy Marie Jehl
Publisher:
ISBN: 9781085729345
Category : Carbon dioxide
Languages : en
Pages : 237
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Book Description
N-heterocyclic carbenes (NHC) are strong Lewis bases that have demonstrated broad utility as ligands for transition metal (TM) catalysts. Silicon analogues, N-heterocyclic silylenes (NHSi), are comparatively less well studied. The decreased [Pi]-[pi] overlap between the Si 3p orbital and adjacent nitrogen lone pairs creates a more accessible vacant orbital on Si, resulting in increased ambiphilic character. When bound to a transition metal, this empty orbital presents an opportunity to cooperatively bind and activate substrate molecules. To increase the stability of a potential metal-silylene complex we targeted the diphosphine ligand precursor 1,2-bis(R2PCH2NCH2)C6H4 (R = alkyl or aryl), first reported by Yamashita and Nozaki in the construction of a boron-anchored pincer. Reported here are (PCy)2Si pincer ligands and their TM-silylene complexes for small molecule activation.
Author: Luke Murphy
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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Book Description
The study of PSiP pincer complexes of second- and third-row transition metals has led to the discovery of challenging bond activation chemistry as well as catalytic chemistry. While there now exists a considerable amount of literature regarding the behavior of PSiP complexes of the second- and third-row metals, comparatively little is known of the behavior of these ligands with the first-row metals. There has been a recent push toward the study of first-row transition metal chemistry in general, due to their high natural abundance and often lower toxicity when compared to their second- and third-row congeners. This document details progress toward the synthesis of a variety of novel Fe, Co and Ni complexes featuring PSiP ligation and application toward catalytic reduction of unsaturated substrates. In terms of (PSiP)Fe chemistry, considerable progress has been made toward the synthesis of novel coordination complexes, in particular the synthesis of hydride complexes of Fe. Organometallic hydride complexes are often implicated as important catalytic intermediates, and in this case a bis(dinitrogen) adduct of an Fe hydride has been identified as a highly active catalyst for the hydrogenation of olefins. Co chemistry with the same ligand has unveiled intriguing examples of both H2 and O2 bond cleavage chemistry, and again has led to an example of an alkene hydrogenation catalyst. A novel PSiP framework has been developed and applied toward chemistry of the group 10 transition metals, particularly nickel. In this regard, chemistry of complexes supported by this new ligand was found to be markedly different than that of similar complexes supported by the previous iteration of the ligand. In particular, a Ni hydride complex was successfully prepared and applied toward the selective reduction of CO2 to the formaldehyde level via hydroboration. Lastly, outside the realm of PSiP chemistry, a new monoanionic P,N-based ligand has been developed and its chemistry has been explored with respect to Fe and Co. Interesting coordination chemistry has been observed with this new ligand, and examples of reactive Fe and Co complexes have been obtained and applied toward the challenging reduction of tertiary amides to amines via catalytic hydrosilylation.
Author: Yu-Peng Zhou
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Book Description
Author: David Morales-Morales
Publisher: Elsevier
ISBN: 0080545157
Category : Science
Languages : en
Pages : 467
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Book Description
Pincer complexes are formed by the binding of a chemical structure to a metal atom with at least one carbon-metal bond. Usually the metal atom has three bonds to a chemical backbone, enclosing the atom like a pincer. The resulting structure protects the metal atom and gives it unique properties.The last decade has witnessed the continuous growth in the development of pincer complexes. These species have passed from being curiosity compounds to chemical chameleons able to perform a wide variety of applications. Their unique metal bound structures provide some of the most active catalysts yet known for organic transformations involving the activation of bonds. The Chemistry of Pincer Compounds details use of pincer compounds including homogeneous catalysis, enantioselective organic transformations, the activation of strong bonds, the biological importance of pincer compounds as potential therapeutic or pharmaceutical agents, dendrimeric and supported materials.* Describes the chemistry and applications of this important class of organometallic and coordination compounds* Covers the areas in which pincer complexes have had an impact* Includes information on more recent and interesting pincer compounds not just those that are well-known
Author: David Morales-Morales
Publisher: Elsevier
ISBN: 0128129328
Category : Science
Languages : en
Pages : 756
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Book Description
Pincer Compounds: Chemistry and Applications offers valuable state-of-the-art coverage highlighting highly active areas of research—from mechanistic work to synthesis and characterization. The book focuses on small molecule activation chemistry (particularly H2 and hydrogenation), earth abundant metals (such as Fe), actinides, carbene-pincers, chiral catalysis, and alternative solvent usage. The book covers the current state of the field, featuring chapters from renowned contributors, covering four continents and ranging from still-active pioneers to new names emerging as creative strong contributors to this fascinating and promising area. Over a decade since the publication of Morales-Morales and Jensen's The Chemistry of Pincer Compounds (Elsevier 2007), research in this unique area has flourished, finding a plethora of applications in almost every single branch of chemistry—from their traditional application as very robust and active catalysts all the way to potential biological and pharmaceutical applications. - Describes the chemistry and applications of this important class of organometallic and coordination compounds - Includes contributions from global leaders in the field, featuring pioneers in the area as well as emerging experts conducting exciting research on pincer complexes - Highlights areas of promising and active research, including small molecule activation, earth abundant metals, and actinide chemistry
Author: Gerhard Erker
Publisher: Springer
ISBN: 364236697X
Category : Science
Languages : en
Pages : 354
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Book Description
Discovery of Frustrated Lewis Pairs: Intermolecular FLPs for Activation of Small Molecules, by Douglas W. Stephan Intramolecular Frustrated Lewis Pairs: Formation and Chemical Features, by Gerald Kehr, Sina Schwendemann, Gerhard Erker Frustrated Lewis Pair Mediated Hydrogenations, by Douglas W. Stephan, Gerhard Erker Amine-Borane Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation, by Victor Sumerin, Konstantin Chernichenko, Felix Schulz, Markku Leskelä, Bernhard Rieger, Timo Repo Hydrogen Activation by Frustrated Lewis Pairs: Insights from Computational Studies, by Tibor András Rokob, Imre Pápai Quantum Chemistry of FLPs and Their Activation of Small Molecules: Methodological Aspects, by Birgitta Schirmer, Stefan Grimme Computational Design of Metal-Free Molecules for Activation of Small Molecules, Hydrogenation, and Hydroamination, by Zhi-Xiang Wang, Lili Zhao, Gang Lu, Haixia Li, Fang Huang Computational Studies of Lewis Acidity and Basicity in Frustrated Lewis Pairs, by Thomas M. Gilbert Solid-State NMR as a Spectroscopic Tool for Characterizing Phosphane - Borane Frustrated Lewis Pairs, by Thomas Wiegand, Hellmut Eckert, Stefan Grimme
Author: Kálmán J. Szabó
Publisher: John Wiley & Sons
ISBN: 3527681337
Category : Science
Languages : en
Pages : 389
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Book Description
This new book on this hot topic summarizes the key achievements for the synthesis and catalytic applications of pincer and pincer-type complexes, providing readers with the latest research highlights. The editors have assembled an international team of leaders in the field, and their contributions focus on the application of various pincer complexes in modern organic synthesis and catalysis, such as C-C and C-X bond forming reactions, C-H bond functionalization, and the activation of small molecules, as well as asymmetric catalysis. A must-have for every synthetic chemist in both academia and industry intending to develop new catalysts and improved synthetic protocols.
Author: Xue Duan
Publisher: Springer
ISBN: 9783540104940
Category : Science
Languages : en
Pages : 204
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Book Description
Author: Thomas P. Fehlner
Publisher: Springer Science & Business Media
ISBN: 1489924590
Category : Science
Languages : en
Pages : 409
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Book Description
There is a certain fascination associated with words. The manipulation of strings of symbols according to mutually accepted rules allows a language to express history as well as to formulate challenges for the future. But language changes as old words are used in a new context and new words are created to describe changing situations. How many words has the computer revolution alone added to languages? "Inorganometallic" is a word you probably have never encountered before. It is one created from old words to express a new presence. A strange sounding word, it is also a term fraught with internal contradiction caused by the accepted meanings of its constituent parts. "In organic" is the name of a discipline of chemistry while "metallic" refers to a set of elements constituting a subsection of that discipline. Why then this Carrollian approach to entitling a set of serious academic papers? Organic, the acknowledged doyenne of chemistry, is distinguished from her brother, inorganic, by the prefix "in," i. e. , he gets everything not organic. Organometallic refers to compounds with carbon-metal bonds. It is simple! Inorganometallic is everything else, i. e. , compounds with noncarbon-metal element bonds. But why a new term? Is not inorganic sufficient? By virtue of training, limited time, resources, co-workers, and so on, chemists tend to work on a specific element class, on a particular compound type, or in a particular phase. Thus, one finds element-oriented chemists (e. g.
Author: Gerard van Koten
Publisher: Springer
ISBN: 3642310818
Category : Science
Languages : en
Pages : 363
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Book Description
Gerard van Koten: The Mono-anionic ECE-Pincer Ligand - a Versatile Privileged Ligand Platform: General Considerations.- Elena Poverenov, David Milstein: Non-Innocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes.- Dean M. Roddick: Tuning of PCP Pincer Ligand Electronic and Steric Properties.- Gemma R. Freeman, J. A. Gareth Williams: Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and Luminescence.- Davit Zargarian, Annie Castonguay, Denis M. Spasyuk: ECE-Type Pincer Complexes of Nickel.- Roman Jambor and Libor Dostál: The Chemistry of Pincer Complexes of 13 - 15 Main Group Elements.- Kálmán J. Szabo: Pincer Complexes as Catalysts in Organic Chemistry.- Jun-ichi Ito and Hisao Nishiyama: Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multi-potent Catalysts.- Anthony St. John, Karen I. Goldberg, and D. Michael Heinekey: Pincer Complexes as Catalysts for Amine Borane Dehydrogenation.- Dmitri Gelman and Ronit Romm: PC(sp3)P Transition Metal Pincer Complexes: Properties and Catalytic Applications.- Jennifer Hawk and Steve Craig: Physical Applications of Pincer Complexes.
