Cooperative Reactivity of Boron-Containing Molecules and Lewis Bases for Metal Free Catalysis

Download Cooperative Reactivity of Boron-Containing Molecules and Lewis Bases for Metal Free Catalysis PDF Online Free

Author :
Publisher :
ISBN 13 :
Total Pages : 210 pages
Book Rating : 4.:/5 (113 download)

DOWNLOAD NOW!


Book Synopsis Cooperative Reactivity of Boron-Containing Molecules and Lewis Bases for Metal Free Catalysis by : Marc-André Légaré

Download or read book Cooperative Reactivity of Boron-Containing Molecules and Lewis Bases for Metal Free Catalysis written by Marc-André Légaré and published by . This book was released on 2015 with total page 210 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition metal catalysis is currently ubiquitous in all sectors of the chemical industry. The reactions it enables allow the production of countless useful chemicals. In the field of organic synthesis alone, the impact and development of catalytic reactions have been recognized several times by the award of Nobel prizes. The use of transition metals for catalysis, however, suffers from several drawbacks that include their high cost, their rarity and their potential toxicity and environmental impact. National and international agencies, as a matter of fact, regulate the trace amounts of residual metal that can be present in many end products. For this reason, there is great interest in discovering alternative catalysts produced from earth-abundant, nontoxic and inexpensive elements. Boron, as a light element of the main group, follows these criteria. The reactivity of organoboron compounds, however, is very different from that of organometallic complexes, and less adapted to typical catalytic process. For this reason, new concepts and new reactions have to be developed in order to introduce boron to the world of catalysis. In order to discover and develop novel ideas towards the design of boron catalysts, we have studied different instances in which Lewis bases influence the reactivity of boron compounds. We hypothesized that the combination of an organoborane and a Lewis base could achieve reactions that would be impossible for the separate units to accomplish. In a first case study, we have investigated in depth the reactivity of neutral adducts of borabenzene towards Lewis bases. We have found that, contrary to usual formulations, borabenzene, under the influence of a Lewis base, reacts as a nucleophile rather than an electrophile. The properties and reactivity of a great number of borabenzene compounds have been studied computationally and experimentally in a work that will be presented in this dissertation. Next, we have studied the reduction of carbon dioxide catalyzed by ambiphilic organoboron compounds. We describe new modes of coordination for boranes with Lewis bases and the application of these interactions to the reduction of CO2 to methanol derivatives. Finally, the culmination of our research efforts is shown as the rational development of a metal-free ambiphilic catalyst for the C-H bond activation and borylation of heteroarenes. In this dissertation, we describe the process by which we designed and implemented this catalytic reaction, as well as the specifics of the system.

Future prospects in boron chemistry: new boron compounds and Lewis acids for catalysis and materials science

Download Future prospects in boron chemistry: new boron compounds and Lewis acids for catalysis and materials science PDF Online Free

Author :
Publisher : OAE Publishing Inc.
ISBN 13 :
Total Pages : 6 pages
Book Rating : 4./5 ( download)

DOWNLOAD NOW!


Book Synopsis Future prospects in boron chemistry: new boron compounds and Lewis acids for catalysis and materials science by : Guillaume Berionni

Download or read book Future prospects in boron chemistry: new boron compounds and Lewis acids for catalysis and materials science written by Guillaume Berionni and published by OAE Publishing Inc.. This book was released on 2021-09-23 with total page 6 pages. Available in PDF, EPUB and Kindle. Book excerpt: Boron-containing compounds have a wide range of structures and rich and multifaceted reactivity patterns. As a result, these compounds are being increasingly used in organometallic, supramolecular, organic and inorganic chemistry, as well as in catalysis and materials science. This perspective describes recent ground-breaking studies and their implications for the future development of new catalysts and materials containing one or several trivalent boron atoms.

Metal-free catalysis using boron-based systems: from designed frustrated Lewis Pairs to boranes

Download Metal-free catalysis using boron-based systems: from designed frustrated Lewis Pairs to boranes PDF Online Free

Author :
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (128 download)

DOWNLOAD NOW!


Book Synopsis Metal-free catalysis using boron-based systems: from designed frustrated Lewis Pairs to boranes by : Julien Légaré Lavergne

Download or read book Metal-free catalysis using boron-based systems: from designed frustrated Lewis Pairs to boranes written by Julien Légaré Lavergne and published by . This book was released on 2021 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Résumé en anglais

Boron-based Lewis Acids

Download Boron-based Lewis Acids PDF Online Free

Author :
Publisher :
ISBN 13 :
Total Pages : 0 pages
Book Rating : 4.:/5 (133 download)

DOWNLOAD NOW!


Book Synopsis Boron-based Lewis Acids by : Jolie Lam

Download or read book Boron-based Lewis Acids written by Jolie Lam and published by . This book was released on 2020 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: A rapid development of metal-free, main group compounds for small molecule activation and as hydrogenation catalysts was triggered after the disclosure of H2 activation by sterically hindered Lewis acids and bases over a decade ago. The combination of a Lewis acid and base with unquenched reactivity was later coined as a "frustrated Lewis pair" (FLP). In this research, boron-based Lewis acids were studied for their application as catalysts in FLP chemistry, with an emphasis on exploring the production of chiral FLPs and intramolecular FLPs. In the exploration towards enantioselective catalysis, 3,5-bicyclic aryl piperidines were synthetically modified to produce B/N FLPs and were shown to activate dihydrogen, demonstrating the potential for expanding chiral FLP templates beyond the typical chiral ligands used in transition metal complexes. Chiral borenium cations were generated from different families of carbene-borane adducts, in which their chirality resides on either the carbene or the borane. Catalytic studies found that they were able to effect imine reduction without epimerisation of the resulting chiral amine, and the reactivity and enantioselectivity of these cations were found to be inversely proportional to steric demands. In the exploration towards a cationic intramolecular FLP, a borenium cation with a pendant phosphine was synthesized through hydroboration of a phosphinoalkene with an isolable B-H borenium cation, and its FLP reactivity was investigated. Finally, initial efforts towards the production of a bisborane-carbene as a tri-functionalized FLP were documented.

Organometallic Pincer Chemistry

Download Organometallic Pincer Chemistry PDF Online Free

Author :
Publisher : Springer
ISBN 13 : 3642310818
Total Pages : 363 pages
Book Rating : 4.6/5 (423 download)

DOWNLOAD NOW!


Book Synopsis Organometallic Pincer Chemistry by : Gerard van Koten

Download or read book Organometallic Pincer Chemistry written by Gerard van Koten and published by Springer. This book was released on 2012-09-17 with total page 363 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Early Main Group Metal Catalysis

Download Early Main Group Metal Catalysis PDF Online Free

Author :
Publisher : John Wiley & Sons
ISBN 13 : 3527344489
Total Pages : 400 pages
Book Rating : 4.5/5 (273 download)

DOWNLOAD NOW!


Book Synopsis Early Main Group Metal Catalysis by : Sjoerd Harder

Download or read book Early Main Group Metal Catalysis written by Sjoerd Harder and published by John Wiley & Sons. This book was released on 2020-04-06 with total page 400 pages. Available in PDF, EPUB and Kindle. Book excerpt: Early Main Group Metal Catalysis gives a comprehensive overview of catalytic reactions in the presence of group 1 and group 2 metals. Chapters are ordered to reaction type, contain educational elements and deal with concepts illustrated by examples that cover the main developments. After a short introduction on polar organometallic chemistry and synthesis of early main group metal complexes, a variety of catalytic reactions are described, e.g. polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, as well as enantioselective and Lewis-acid catalysis. The book addresses organic chemists and researchers in industry interested in the state-of-the-art and new possibilities of early main group metal catalysis as well as newcomers to the field. Written by a team of leaders in the field, it is a very welcome addition to the area of main group metal chemistry, and to the field of catalysis.

Organometallic Chemistry

Download Organometallic Chemistry PDF Online Free

Author :
Publisher : Royal Society of Chemistry
ISBN 13 : 1788012208
Total Pages : 171 pages
Book Rating : 4.7/5 (88 download)

DOWNLOAD NOW!


Book Synopsis Organometallic Chemistry by : Ian Fairlamb

Download or read book Organometallic Chemistry written by Ian Fairlamb and published by Royal Society of Chemistry. This book was released on 2017-07-25 with total page 171 pages. Available in PDF, EPUB and Kindle. Book excerpt: With the increase in volume, velocity and variety of information, researchers can find it difficult to keep up to date with the literature in their field. This interdisciplinary field has the potential to provide answers to problems and challenges faced in catalysis, synthetic organic chemistry and the development of therapeutic agents and new materials. Providing an invaluable volume, Organometallic Chemistry Volume 41 contains analysed, evaluated and distilled information on the latest in organometallic chemistry research including developments and applications of Lewis acidic boron reagents, masked low-coordinate main group species in synthesis and the diiron centre.

Applied Homogeneous Catalysis with Organometallic Compounds

Download Applied Homogeneous Catalysis with Organometallic Compounds PDF Online Free

Author :
Publisher : John Wiley & Sons
ISBN 13 : 3527328971
Total Pages : 1778 pages
Book Rating : 4.5/5 (273 download)

DOWNLOAD NOW!


Book Synopsis Applied Homogeneous Catalysis with Organometallic Compounds by : Boy Cornils

Download or read book Applied Homogeneous Catalysis with Organometallic Compounds written by Boy Cornils and published by John Wiley & Sons. This book was released on 2017-12-26 with total page 1778 pages. Available in PDF, EPUB and Kindle. Book excerpt: The completely revised third edition of this four-volume classic is fully updated and now includes such topics as as CH-activation and multicomponent reactions. It describes the most important reaction types, new methods and recent developments in catalysis. The internationally renowned editors and a plethora of international authors (including Nobel laureate R. Noyori) guarantee high quality content throughout the book. A "must read" for everyone in academia and industry working in this field.

Boronic Acids

Download Boronic Acids PDF Online Free

Author :
Publisher : John Wiley & Sons
ISBN 13 : 3527606823
Total Pages : 571 pages
Book Rating : 4.5/5 (276 download)

DOWNLOAD NOW!


Book Synopsis Boronic Acids by : Dennis G. Hall

Download or read book Boronic Acids written by Dennis G. Hall and published by John Wiley & Sons. This book was released on 2006-05-12 with total page 571 pages. Available in PDF, EPUB and Kindle. Book excerpt: For the first time, the whole field of organoboronic acids is presented in one comprehensive handbook. Professor Dennis Hall, a rising star within the community, covers all aspects of this important substance class, including applications in chemistry, biology and medicine. Starting with an introduction to the structure, properties, and preparation of boronic acid derivatives, together with an overview of their reactions and applications, the book goes on to look at metal-catalyzed borylation of alkanes and arenas, coupling reactions and rhodium-catalyzed additions of boronic acids to alkenes and carbonyl compounds. There follows chapters on copper-promoted C-O and C-N cross-coupling of boronic acids, recent applications in organic synthesis, as well as alpha-haloalkylboronic esters in asymmetric synthesis. Later sections deal with cycloadditions, organoboronic acids, oxazaborolidines as asymmetric inducers, and boronic acid based receptors and sensors. The whole is rounded off with experimental procedures, making this invaluable reading for organic, catalytic and medicinal chemists, as well as those working in organometallics.

Synthesis of Boron, Silicon, and Phosphorus Lewis Acids and Frustrated Lewis Pair Complexes for C

Download Synthesis of Boron, Silicon, and Phosphorus Lewis Acids and Frustrated Lewis Pair Complexes for C PDF Online Free

Author :
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (133 download)

DOWNLOAD NOW!


Book Synopsis Synthesis of Boron, Silicon, and Phosphorus Lewis Acids and Frustrated Lewis Pair Complexes for C by : Ian Robert Faulkner Mallov

Download or read book Synthesis of Boron, Silicon, and Phosphorus Lewis Acids and Frustrated Lewis Pair Complexes for C written by Ian Robert Faulkner Mallov and published by . This book was released on 2017 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The recent proliferation of main group catalysts and stoichiometric reagents useful in effecting transformations of organic molecules has been augmented by development of the chemistry of frustrated Lewis pairs (FLPs). In seeking to both complement and emulate the reactivity of transition metal catalysts, both the synthesis of new Lewis acids and FLPs and the discovery of new reactivity with organic substrates has been explored. Boron Lewis acids such as B(C6F5)3 and electrophilic borenium cations are among the most commonly employed main group catalysts, particularly for the hydrogenation of unsaturated bonds. The first chapter of this thesis details explorations in modulating the Lewis acidity of neutral and cationic boron electrophiles by tuning phosphinimine and phosphine-amine ligands. A family of compounds featuring a P-N-B motif are presented. In seeking to broaden the range of main group catalysts, phosphorus Lewis acids have been explored. The third and fourth chapters presented herein detail the synthesis and catalytic activity of electrophilic phosphonium cations (EPCs). Synthesis of a chloride-substituted dication, and ferrocenyl-based mono- and dications are described, with a particular emphasis on their catalytic activity in the deoxygenation of ketones. The fifth chapter details the synthesis of phosphorus cations which attempt to model intermediates in EPC-mediated catalysis. Silylium cations are strongly fluorophilic and have previously been shown to cleave aliphatic C-F bonds. The final chapter presents examples of silylium cations in combination with weak phosphine Lewis bases for the selective cleavage of one C-F bond of an aryl-CF3 functionality. The FLP-captured PhCF2 is then converted to PhCF2H, completing a formal hydrodefluorination process of PhCF3 to PhCF2H. Analogous reactivity is observed with aryl-CF2 compounds.

Frustrated Lewis Pairs II

Download Frustrated Lewis Pairs II PDF Online Free

Author :
Publisher : Springer
ISBN 13 : 3642377599
Total Pages : 321 pages
Book Rating : 4.6/5 (423 download)

DOWNLOAD NOW!


Book Synopsis Frustrated Lewis Pairs II by : Gerhard Erker

Download or read book Frustrated Lewis Pairs II written by Gerhard Erker and published by Springer. This book was released on 2013-12-12 with total page 321 pages. Available in PDF, EPUB and Kindle. Book excerpt: Frustrated Lewis Pairs: From Dihydrogen Activation to Asymmetric Catalysis, by Dianjun Chen, Jürgen Klankermayer Coexistence of Lewis Acid and Base Functions: A Generalized View of the Frustrated Lewis Pair Concept with Novel Implications for Reactivity, by Heinz Berke, Yanfeng Jiang, Xianghua Yang, Chunfang Jiang, Subrata Chakraborty, Anne Landwehr New Organoboranes in "Frustrated Lewis Pair" Chemistry, by Zhenpin Lu, Hongyan Ye, Huadong Wang Paracyclophane Derivatives in Frustrated Lewis Pair Chemistry, by Lutz Greb, Jan Paradies Novel Al-Based FLP Systems, by Werner Uhl, Ernst-Ulrich Würthwein N-Heterocyclic Carbenes in FLP Chemistry, by Eugene L. Kolychev, Eileen Theuergarten, Matthias Tamm Carbon-Based Frustrated Lewis Pairs, by Shabana Khan, Manuel Alcarazo Selective C-H Activations Using Frustrated Lewis Pairs. Applications in Organic Synthesis, by Paul Knochel, Konstantin Karaghiosoff, Sophia Manolikakes FLP-Mediated Activations and Reductions of CO2 and CO, by Andrew E. Ashley, Dermot O’Hare Radical Frustrated Lewis Pairs, by Timothy H. Warren and Gerhard Erker Polymerization by Classical and Frustrated Lewis Pairs, by Eugene Y.-X. Chen Frustrated Lewis Pairs Beyond the Main Group: Transition Metal-Containing Systems, by D. Wass Reactions of Phosphine-Boranes and Related Frustrated Lewis Pairs with Transition Metal Complexes, by Abderrahmane Amgoune, Ghenwa Bouhadir, Didier Bourissou

Anion Receptor Chemistry

Download Anion Receptor Chemistry PDF Online Free

Author :
Publisher : Royal Society of Chemistry
ISBN 13 : 1847552471
Total Pages : 431 pages
Book Rating : 4.8/5 (475 download)

DOWNLOAD NOW!


Book Synopsis Anion Receptor Chemistry by : Jonathan L Sessler

Download or read book Anion Receptor Chemistry written by Jonathan L Sessler and published by Royal Society of Chemistry. This book was released on 2007-10-31 with total page 431 pages. Available in PDF, EPUB and Kindle. Book excerpt: Anion recognition plays a critical role in a range of biological processes, and a variety of receptors and carriers can be found throughout the natural world. Chemists working in the area of supramolecular chemistry have created a range of anion receptors, drawing inspiration from nature as well as their own inventive processes. This book traces the origins of anion recognition chemistry as a unique sub-field in supramolecular chemistry while illustrating the basic approaches currently being used to effect receptor design. The combination of biological overview and summary of current synthetic approaches provides a coverage that is both comprehensive and comprehensible. First, the authors detail the key design motifs that have been used to generate synthetic receptors and which are likely to provide the basis for further developments. They also highlight briefly some of the features that are present in naturally occurring anion recognition and transport systems and summarise the applications of anion recognition chemistry. Providing as it does a detailed review for practitioners in the field and a concise introduction to the topic for newcomers, Anion Receptor Chemistry reflects the current state of the art. Fully referenced and illustrated in colour, it is a welcome addition to the literature.

Pinch Me If You Can

Download Pinch Me If You Can PDF Online Free

Author :
Publisher :
ISBN 13 : 9781087076188
Total Pages : 122 pages
Book Rating : 4.0/5 (761 download)

DOWNLOAD NOW!


Book Synopsis Pinch Me If You Can by : My Unique Books

Download or read book Pinch Me If You Can written by My Unique Books and published by . This book was released on 2019-08-02 with total page 122 pages. Available in PDF, EPUB and Kindle. Book excerpt: Get prepared for the upcoming school year and get organized with this notepad. A great place to record the main important information of your class, lecture or meeting and to create a to-do list. PICK THIS PRODUCT NOW! Perfect for girls or boys, this notebook can also be used as a diary. Features: ample room for notes on lined journal pages. Product description: 5 x 8; 120 pages of lined paper, uniquely designed matte cover. We have lots of great notebooks, sheet music, planners and journals, so be sure to check out our other listings by clicking on the "Author Name" link just below the title of this tracker. Ideas on how to use this journal: back to school shopping; high school student gift; middle school student present; teacher supplies for university and college; pupils who like sketching and doodling.

Boron-ligand Cooperation

Download Boron-ligand Cooperation PDF Online Free

Author :
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (116 download)

DOWNLOAD NOW!


Book Synopsis Boron-ligand Cooperation by : Urs Gellrich

Download or read book Boron-ligand Cooperation written by Urs Gellrich and published by . This book was released on 2017 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: In recent years, metal-ligand cooperation has emerged as a powerful tool for sigma-bond activation by transition-metal complexes. We report the synthesis of a pyridone borane complex that liberates dihydrogen under mild conditions. The reverse reaction, dihydrogen activation by the formed pyridonate borane complex, is achieved under moderate H2 pressure at room temperature (Figure 1a). Significantly, computations and experiments show that the boroxypyridine undergoes a chemical transformation to a neutral pyridone donor ligand in the course of the hydrogen activation. This unprecedented mode of action may thus, in analogy to metal-ligand cooperation, be regarded as an example of boron-ligand cooperation. The unique reactivity of this system and the first applications in metal-free catalysis will be presented. Recently, we found that a sterically encumbered thiopyridone catalysis the dehydrogenation of ammonia-borane with high efficiency (Figure 1b). The key step of the catalytic transformation is an inorganic retro-ene reaction, which can be described as an example of intramolecular boron-ligand cooperation.

The Activation of Small Molecules Employing Main Group and Transition Metal Frustrated Lewis Pairs

Download The Activation of Small Molecules Employing Main Group and Transition Metal Frustrated Lewis Pairs PDF Online Free

Author :
Publisher :
ISBN 13 :
Total Pages : 536 pages
Book Rating : 4.:/5 (824 download)

DOWNLOAD NOW!


Book Synopsis The Activation of Small Molecules Employing Main Group and Transition Metal Frustrated Lewis Pairs by : Rebecca Claire Neu

Download or read book The Activation of Small Molecules Employing Main Group and Transition Metal Frustrated Lewis Pairs written by Rebecca Claire Neu and published by . This book was released on 2012 with total page 536 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Synthetic Inorganic Chemistry

Download Synthetic Inorganic Chemistry PDF Online Free

Author :
Publisher : Elsevier
ISBN 13 : 0128189339
Total Pages : 525 pages
Book Rating : 4.1/5 (281 download)

DOWNLOAD NOW!


Book Synopsis Synthetic Inorganic Chemistry by : Ewan J. M. Hamilton

Download or read book Synthetic Inorganic Chemistry written by Ewan J. M. Hamilton and published by Elsevier. This book was released on 2021-04-17 with total page 525 pages. Available in PDF, EPUB and Kindle. Book excerpt: Synthetic Inorganic Chemistry: New Perspectives presents summaries of the work of some of the most creative researchers in the field. The book highlights the most novel approaches and burgeoning applications of synthetic inorganic chemistry in development. Topics include non-precious metals in catalysis, smart inorganic polymers, new inorganic therapeutics, new photocatalysts for hydrogen production, and more. As the first volume in the Developments in Inorganic Chemistry series, this work is a valuable resource for students and researchers working in inorganic chemistry and material science. Illustrates the scope and vitality of modern synthetic inorganic chemistry Shows the centrality of inorganic chemistry, addressing a variety of global challenges Serves to define the current, important and expanding roles of synthetic inorganic chemistry in interdisciplinary areas such as materials science, synthetic organic chemistry, homogeneous and heterogeneous catalysis

Pincer and Pincer-Type Complexes

Download Pincer and Pincer-Type Complexes PDF Online Free

Author :
Publisher : John Wiley & Sons
ISBN 13 : 3527681337
Total Pages : 389 pages
Book Rating : 4.5/5 (276 download)

DOWNLOAD NOW!


Book Synopsis Pincer and Pincer-Type Complexes by : Kálmán J. Szabó

Download or read book Pincer and Pincer-Type Complexes written by Kálmán J. Szabó and published by John Wiley & Sons. This book was released on 2014-06-10 with total page 389 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.