Metal-ligand Multiple Bonds as Single Atom Sources for the Assembly of New Ligands PDF Download
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Author: Jorge L. Martinez (Chemist)
Publisher:
ISBN:
Category : Ligands (Biochemistry)
Languages : en
Pages : 224
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Book Description
Atom transfer reactions such as HAT (hydrogen atom transfer) and OAT (oxygen atom transfer) offer a method for efficient bond formation in a single step. Extending this concept, this single atom delivery also has the potential to provide an effective route to otherwise inaccessible ligands. In this work, we investigate the utility of the tris(carbene)borate iron(IV) nitride, PhB(iPr2Im)3Fe≡N, as a viable nitrogen atom source for the assembly of new ligands. In one embodiment of this approach, an unusual carbon atom transfer reaction leads to the assembly of a C≡N− ligand when two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) carbene are added to PhB(iPr2Im)3Fe≡N. This strategy is extended to access of the elusive gas molecule, P≡N, which is assembled by using (N3N)Mo≡P (N3N = [N(CH2CH2NSiMe3)3]3−) and PhB(iPr2Im)3Fe≡N as P- and N-atom sources, respectively. These are the first structurally characterized compounds with this unique ligand. Photoisomerization of the P≡N ligand is observed in the solid-state and trapping of the N≡P linkage isomer reveals the fluxionality of this ligand in solution. Additionally, the bis(carbene)borate ligand framework is also explored as supporting ligand for the development of new metal-ligand multiply bonded complexes with the first structural characterization of an Fe(VI) compound, the highest oxidation state of iron, being achieved.
Author: Jorge L. Martinez (Chemist)
Publisher:
ISBN:
Category : Ligands (Biochemistry)
Languages : en
Pages : 224
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Book Description
Atom transfer reactions such as HAT (hydrogen atom transfer) and OAT (oxygen atom transfer) offer a method for efficient bond formation in a single step. Extending this concept, this single atom delivery also has the potential to provide an effective route to otherwise inaccessible ligands. In this work, we investigate the utility of the tris(carbene)borate iron(IV) nitride, PhB(iPr2Im)3Fe≡N, as a viable nitrogen atom source for the assembly of new ligands. In one embodiment of this approach, an unusual carbon atom transfer reaction leads to the assembly of a C≡N− ligand when two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) carbene are added to PhB(iPr2Im)3Fe≡N. This strategy is extended to access of the elusive gas molecule, P≡N, which is assembled by using (N3N)Mo≡P (N3N = [N(CH2CH2NSiMe3)3]3−) and PhB(iPr2Im)3Fe≡N as P- and N-atom sources, respectively. These are the first structurally characterized compounds with this unique ligand. Photoisomerization of the P≡N ligand is observed in the solid-state and trapping of the N≡P linkage isomer reveals the fluxionality of this ligand in solution. Additionally, the bis(carbene)borate ligand framework is also explored as supporting ligand for the development of new metal-ligand multiply bonded complexes with the first structural characterization of an Fe(VI) compound, the highest oxidation state of iron, being achieved.
Author: William A. Nugent
Publisher: Wiley-Interscience
ISBN:
Category : Science
Languages : en
Pages : 360
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Book Description
The only comprehensive one-volume text/reference on metal-ligand multiple bonds. Stresses the unified nature of the field and includes handy new tabulations of data. The flow within each subtopic is oxygen to nitrogen to carbon. Coverage is up-to-date--virtually every subtopic leads to interesting questions for future research. Presents information otherwise scattered through hundreds of publications.
Author: F. Albert Cotton
Publisher: Springer Science & Business Media
ISBN: 0387258299
Category : Science
Languages : en
Pages : 840
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Book Description
Provides historical perspective as well as current data Abundantly illustrated with figures redrawn from literature data Covers all pertinent theory and physical chemistry Catalytic and chemotherapeutic applications are included
Author: Keith Searles
Publisher:
ISBN:
Category : Catalysts
Languages : en
Pages : 254
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Book Description
Author: Vlad Mihai Iluc
Publisher:
ISBN:
Category : Nickel
Languages : en
Pages : 550
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Book Description
Author: Françoise Colobert
Publisher: John Wiley & Sons
ISBN: 3527343407
Category : Science
Languages : en
Pages : 294
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Book Description
Provides, in one handbook, comprehensive coverage of one of the hottest topics in stereoselective chemistry Written by leading international authors in the field, this book introduces readers to C-H activation in asymmetric synthesis along with all of its facets. It presents stereoselective C-H functionalization with a broad coverage, from outer-sphere to inner-sphere C-H bond activation, and from the control of olefin geometry to the induction of point, planar and axial chirality. Moreover, methods wherein asymmetry is introduced either during the C-H activation or in a different elementary step are discussed. Presented in two parts?asymmetric activation of C(sp3)-H bonds and stereoselective synthesis implying activation of C(sp2)-H bonds?CH-Activation for Asymmetric Synthesis showcases the diversity of stereogenic elements, which can now be constructed by C-H activation methods. Chapters in Part 1 cover: C(sp3)-H bond insertion by metal carbenoids and nitrenoids; stereoselective C-C bond and C-N bond forming reactions through C(sp3)?H bond insertion of metal nitrenoids; enantioselective intra- and intermolecular couplings; and more. Part 2 looks at: C-H activation involved in stereodiscriminant step; planar chirality; diastereoselective formation of alkenes through C(sp2)?H bond activation; amongst other methods. -Covers one of the most rapidly developing fields in organic synthesis and catalysis -Clearly structured in two parts (activation of sp3- and activation of sp2-H bonds) -Edited by two leading experts in C-H activation in asymmetric synthesis CH-Activation for Asymmetric Synthesis will be of high interest to chemists in academia, as well as those in the pharmaceutical and agrochemical industry.
Author: R. M. Diamond
Publisher:
ISBN:
Category : Actinide elements
Languages : en
Pages : 46
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Book Description
A study has been made of the elution behavior of curium(III), americium(III), plutonium(III), actinium(III), plutonium(IV), neptunium(IV), uraniuM(IV), thorium(IV), neptunium(V), plutonium (VI), uranium (VI), lanthanum(III), cerium(III), europium(III), ytterbium(III), ytterium(III), strontium(II), barium(II), radium(II), cesium(I) with 3.2 M, 6.2 M, 9.3 M, and 12.2 M HCl solutions from Dowex-50 cation exchange resin columns. These elutions show that in high concentrations of hydrochloric acid the actinides form complex ions with chloride ion to a much greater extent than the lanthanides. The strengths of the tripositive actinide complex ions apparently go in the order plutonium > americium> curium, although their ionic radii also decrease in this same order. To explain these results, a partial covalent character may be ascribed to the bonding in the transuranium complex ions. It is shown that a reasonable structure for such covalent bonding involves hybridization of the 5f orbitals in the actinide elements.
Author: Yves Canac
Publisher: Mdpi AG
ISBN: 9783036513508
Category :
Languages : en
Pages : 312
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Book Description
Homogeneous catalysis owes its success, in large part, to the development of a wide range of ligands with well-defined electronic and steric properties, which have thus made it possible to adjust the behavior of many organometallic complexes. However, ligands used in catalysis have long been centered on elements of group 15, and it is only more recently that carbon ligands have proved to be valuable alternatives with the emergence of cyclic diaminocarbenes (NHC).This Special Issue aims to provide a contemporary overview of the advances in carbon ligand chemistry from fundamental aspects to applications.
Author:
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 778
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Book Description
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
