skip to content
Metal dihydrogen and [sigma]-bond complexes Preview this item
ClosePreview this item
Checking...

Metal dihydrogen and [sigma]-bond complexes

Author: Gregory J Kubas
Publisher: New York : Kluwer Academic/Plenum Publishers, ©2001.
Series: Modern inorganic chemistry.
Edition/Format:   Print book : EnglishView all editions and formats
Summary:

Covers Kubas' discovery of dihydrogen coordination and the study of its structure and general properties. This book also discusses both the theoretical beliefs and experimental results of bonding and  Read more...

Rating:

(not yet rated) 0 with reviews - Be the first.

Subjects
More like this

Find a copy online

Links to this item

Find a copy in the library

&AllPage.SpinnerRetrieving; Finding libraries that hold this item...

Details

Material Type: Internet resource
Document Type: Book, Internet Resource
All Authors / Contributors: Gregory J Kubas
ISBN: 0306464659 9780306464652
OCLC Number: 123148269
Description: xvi, 472 pages : illustrations ; 26 cm.
Contents: 1.1. Nonclassical Bonding in [sigma] Complexes 1 --
1.2. Small-Molecule Activation on Transition Metal Complexes 5 --
1.3. [sigma] Complexes As "Arrested Intermediates" along the Reaction Coordinate for [sigma]-Bond Cleavage 7 --
1.4. Importance of Backdonation in [sigma]-Bond Coordination and Cleavage 10 --
1.5. Reactivity of [sigma]-Complexes: [sigma]-Bond Metathesis, Acidity, and Heterolytic Cleavage of X-H Bonds 12 --
2. Background and Discovery of Dihydrogen Coordination 17 --
2.1. Homogeneous Activation of Dihydrogen on Metal Complexes 17 --
2.2. Discovery of Dihydrogen Complexes 20 --
2.2.2. Discovery of Dihydrogen Coordination 24 --
2.2.3. Development of Dihydrogen Coordination Chemistry 29 --
3. Synthesis and General Properties of Dihydrogen Complexes 33 --
3.1 Stable Dihydrogen Complexes 33 --
3.1.3. Complexes Synthesized by Addition of H[subscript 2] Gas to an Unsaturated Precursor 42 --
3.1.4. Complexes Prepared from H[subscript 2] Gas by Ligand Displacement or Reduction 45 --
3.1.5. Protonation of a Hydride Complex 46 --
3.1.6. Other Methods of Preparation 47 --
3.2. Dihydrogen Complexes Unstable at Room Temperature 48 --
3.2.1. Organometallic Complexes Observed at Low Temperature in Rare Gas or Other Media 48 --
3.2.2. Binding of H[subscript 2] to Bare Metal Atoms, Ions, and Surfaces 50 --
4. Bonding and Activation of Dihydrogen and [sigma] Ligands: Theory versus Experiment 59 --
4.2. Development of the Theoretical Aspects of Metal-Dihydrogen Bonding and Calculational Methodologies 61 --
4.3. Theoretical Studies of Oxidative Addition of Dihydrogen 63 --
4.4. Palladium (Dihydrogen)--The First Prediction of a Stable Dihydrogen Complex 67 --
4.5. Theoretical Studies of M(CO)[subscript 3](PR[subscript 3])[subscript 2](H[subscript 2]) and Bonding Model for Dihydrogen Coordination 69 --
4.6. Relative Strengths of Dihydrogen as a [pi] Acceptor and as a Donor Ligand Compared to Other Ligands 75 --
4.7. Dihydrogen versus Dihydride Coordination: Activation of Dihydrogen toward Oxidative Addition 79 --
4.7.1. Crucial Influence of the Ligand trans to H[subscript 2] 81 --
4.7.2. Other Ligand/Metal/Charge Effects on H[subscript 2] Binding and Activation: Why FeH[subscript 2](CO)[subscript 4] Is a Dihydride 84 --
4.7.3. Reaction Coordinate for OA: The Point at Which the H-H Bond Is Broken 88 --
4.7.4. Elongated Dihydrogen Complexes: Extraordinarily Delocalized Dynamic Systems 97 --
4.7.5. Further Aspects of Electronic and Steric Control of Dihydrogen versus Dihydride Bonding 104 --
4.8. Polyhydride-Dihydrogen Complexes 107 --
4.9. Cp and Tp Complexes, Including d[superscript 0] Systems 111 --
4.10. Polyhydride Complexes with CO versus Halide Ligands 114 --
4.11. Interaction of a Coordinated [sigma] Bond with a cis Ligand: The cis Effect in Hydride-Dihydrogen Complexes 115 --
4.12. Intramolecular Hydrogen Exchange, Polyhydrogen Complexes, and [sigma]-Bond Metathesis 121 --
4.13. Dihydrogen and Methane Binding to Naked Metal Ions 128 --
4.14. Interaction of Dihydrogen with Metal Surfaces, Metal Oxides and Hydrides, and Nontransition Metal Systems 131 --
5. Structural and NMR Studies of Dihydrogen Complexes 143 --
5.2. Diffraction Methods 145 --
5.3. Solid State NMR 148 --
5.4. Solution NMR: J[subscript HD] Coupling and Isotope Effects 150 --
5.5. NMR Relaxation Time T[subscript 1], Deuterium Quadrupole Coupling, and Effects of Dihydrogen Rotation 158 --
5.6. H-H Distance and Other Crystallographic and Structural Aspects of Dihydrogen Coordination 164 --
6. Intramolecular Dynamics of Dihydrogen-Hydride Ligand Systems: Hydrogen Rotation, Exchange, and Quantum-Mechanical Effects 171 --
6.2. Dihydrogen Rotation in M([eta superscript 2]-H[subscript 2]) 173 --
6.2.1. Determination of the Barrier to Rotation of H[subscript 2] 174 --
6.2.2. Inelastic Neutron Scattering 176 --
6.2.3. Origin of the Barrier to Rotation of [eta superscript 2]-H[subscript 2] 178 --
6.2.3.1. Metal-Hydrogen Binding 178 --
6.2.3.2. Effect of the Metal Center 179 --
6.2.3.3. Ligand Effects 182 --
6.2.3.4. Intramolecular Interactions and Crystal Packing Effects 184 --
6.2.4. Two-Dimensional Parameterized Model for H[subscript 2] Rotation 186 --
6.3. Intramolecular Hydrogen Rearrangement and Exchange 187 --
6.3.1. Extremely Facile Hydrogen Exchange in IrXH[subscript 2](H[subscript 2])(PR[subscript 3])[subscript 2] and Related Systems 190 --
6.3.2. Other Systems that Exchange Hydrogens in H[subscript 2] and Hydride Ligands 192 --
6.3.3. Quasi-Elastic Neutron Scattering Studies of H[subscript 2] Exchange with cis Hydrides 194 --
6.3.4. Quantum-Mechanical Exchange Coupling and Hindered Rotational Phenomena 198 --
7. Thermodynamics, Kinetics, and Isotope Effects of the Binding and Cleavage of [sigma] Ligands versus Classical Ligands 207 --
7.1. Themodynamics of Dihydrogen and [sigma]-Bond Coordination to Metal Centers 207 --
7.1.1. Binding Energies of H[subscript 2] and [sigma] Ligands to Stable Complexes 207 --
7.1.2. Binding Energies of H[subscript 2] and [sigma] Ligands to Thermally Unstable Metal Complexes 210 --
7.2. Binding Strength of Dihydrogen and [sigma] Ligands versus Classical Ligands; Importance of Entropy 213 --
7.3. Kinetics of Formation and Substitution of Dihydrogen, Alkane, and Related [sigma] Ligands 222 --
7.4. Reaction Profiles and Kinetics for Coordination and Oxidative Addition of Dihydrogen and Other [sigma] Ligands 226 --
7.5. Isotope Effects in [sigma]-Ligand Coordination and Oxidative Addition 233 --
7.5.1. Equilibrium Isotope Effects for H[subscript 2] versus D[subscript 2] Binding 234 --
7.5.2. Origin of the Inverse EIE for H[subscript 2] and Other [sigma]-Ligand Binding and EIE for OA 235 --
7.5.3. Kinetic Isotope Effects for H[subscript 2] and Alkane OA and Reductive Elimination 238 --
8. Vibrational Studies of Coordinated Dihydrogen 245 --
8.1. Vibrational Modes for [eta superscript 2]-H[subscript 2] 245 --
8.2. Normal Coordinate Analysis of W(H[subscript 2])(CO)[subscript 3](PCy[subscript 3])[subscript 2] 249 --
8.3. Bonding Character of Dihydrogen Complexes Suggested by Vibrational Analysis 253 --
8.4. Highly Mixed H-H and M-H[subscript 2] Modes in Elongated Dihydrogen Complexes: New Normal-Mode Definitions 255 --
9. Reactions and Acidity of Dihydrogen Complexes 259 --
9.2. Homolytic Splitting of Coordinated Dihydrogen 261 --
9.3. Isotopic Exchange and Other Intramolecular Hydrogen Exchange Reactions 265 --
9.4. Heterolytic Cleavage and Acidity of Coordinated Dihydrogen 270 --
9.4.2. Thermodynamic and Kinetic Acidity of H[subscript 2] Ligands 273 --
9.4.3. Intermolecular Heterolytic Cleavage of Coordinated H[subscript 2] 278 --
9.4.4. Intramolecular Heterolytic Cleavage 280 --
9.4.4.1. Proton Transfer to Ancillary Ligands and H[subscript 2] Bonding 280 --
9.4.4.2. Proton Transfer to Anions 283 --
9.5. Catalytic Hydrogenation and Related Reactions 284 --
9.5.1. Direct Transfer of Hydrogen from H[subscript 2] Ligands 284 --
9.5.2. H[subscript 2] Complexes as Precursors for Catalytic and Other Reactions 288 --
9.5.3. Ionic Hydrogenation and Zeolite-Catalyzed Hydrogenation 290 --
10. Activation of Hydrogen and Related Small Molecules by Metalloenzymes and Sulfur Ligand Systems 297 --
10.1. Hydrogenases: Biorganometallic Formation and Splitting of Dihydrogen 297 --
10.1.2. [NiFe] H-ases 300 --
10.1.3. A Metal-Free Hydrogenase 306 --
10.1.4. [Fe] Hydrogenases: Highly Organometallic Active Sites 307 --
10.2. Nitrogenases and Nitrogen Fixation 312 --
10.3. Hydrocarbon Activation by Oxygenase Enzymes 316 --
10.4. Models for Biological and Industrial Activation of Hydrogen on Sulfur Ligands and Sulfides 319 --
11. Coordination and Activation of Si-H, Ge-H, and Sn-H Bonds 327 --f 11.2. Synthesis and Characterization of M([eta superscript 2]-Si-H) Complexes 330 --
11.3. Si-H Bonding to Metals Compared to M-H[subscript 2] Bonding 342 --
11.3.1. Comparisons of H-H versus Si-H [sigma]-Bond Activation and OA Processes 344 --
11.3.2. Theoretical Studies of Si-H versus H-H [sigma]-Bond Activation 349 --
11.4. Reactions and Dynamics of [sigma]-Silane Complexes 352 --
11.4.1. Heterolytic Cleavage of M([eta superscript 2]-Si-H) and Related Reactions 353 --
11.4.2. Dynamics of Silane Ligands and Exchange with cis Hydrides 355 --
11.5. Germane and Stannane [sigma] Complexes 357 --
12. C-H Bond Coordination and Activation 365 --
12.2. Agostic C-H Coordination and Cyclometallation 367 --
12.2.1. Structures and Strengths of M ... H-C Interaction 367 --
12.2.2. Cyclometallation and Oxidative Addition of Agostic C-H Bonds 374 --
12.2.3. Agostic Interactions in Phosphine Complexes 378 --
12.3. Alkane Coordination 383 --
12.3.1. Experimental Evidence 383 --
12.3.2. Theoretical Studies of Alkane Activation and C-H versus C-F Bond Coordination 388 --
12.4. Evidence for [sigma] Complexes in the Oxidative Addition and Reductive Elimination of C-H Bonds 395 --
12.4.1. Isotopic Exchange in Intermediates in RE and OA of Alkanes and Other Transformations 395 --
12.4.2. Direct Spectroscopic Evidence for Alkane Complexes as Intermediates in OA of Alkanes 399 --
12.4.3. Shilov Chemistry and Related Electrophilic Systems for Homogeneous Alkane Oxidation 403 --
13. Coordination and Activation of B-H and Other X-H and X-Y Bonds 417 --
13.1. B-H Bonds 417 --
13.1.1. Metal Borohydride and Agostic-Like Systems 417 --
13.1.2. [sigma] Complexes of Neutral Boranes 421 --
13.2. X-H [sigma] Interactions Where X Is Also a Lone-Pair Donor (N, P, S) 429 --
13.3. Interactions of [sigma] Bonds X-Y Where X and Y Are Not Hydrogen 431 --
13.3.1. C-Halogen Bonds 431.
Series Title: Modern inorganic chemistry.
Responsibility: Gregory J. Kubas.

Reviews

Editorial reviews

Publisher Synopsis

`[This book] will remain a classic for researchers, professors, and students and a must for everyone working in organometallic Chemistry and Catalysis.' Bruno Chaudret, Director de Recherche, Read more...

 
User-contributed reviews
Retrieving GoodReads reviews...
Retrieving DOGObooks reviews...

Tags

Be the first.

Similar Items

Confirm this request

You may have already requested this item. Please select Ok if you would like to proceed with this request anyway.

Linked Data


Primary Entity

<http://www.worldcat.org/oclc/123148269> # Metal dihydrogen and [sigma]-bond complexes
    a schema:Book, schema:CreativeWork ;
   library:oclcnum "123148269" ;
   library:placeOfPublication <http://dbpedia.org/resource/New_York_City> ; # New York
   library:placeOfPublication <http://id.loc.gov/vocabulary/countries/nyu> ;
   schema:about <http://id.worldcat.org/fast/852856> ; # Chemical bonds
   schema:about <http://id.worldcat.org/fast/1017569> ; # Metal complexes
   schema:about <http://dewey.info/class/541.2242/e21/> ;
   schema:about <http://id.worldcat.org/fast/964990> ; # Hydrogen
   schema:bookFormat bgn:PrintBook ;
   schema:copyrightYear "2001" ;
   schema:creator <http://viaf.org/viaf/74067953> ; # Gregory J. Kubas
   schema:datePublished "2001" ;
   schema:exampleOfWork <http://worldcat.org/entity/work/id/341648136> ;
   schema:inLanguage "en" ;
   schema:isPartOf <http://experiment.worldcat.org/entity/work/data/341648136#Series/modern_inorganic_chemistry> ; # Modern inorganic chemistry.
   schema:name "Metal dihydrogen and [sigma]-bond complexes"@en ;
   schema:productID "123148269" ;
   schema:publication <http://www.worldcat.org/title/-/oclc/123148269#PublicationEvent/new_york_kluwer_academic_plenum_publishers_2001> ;
   schema:publisher <http://experiment.worldcat.org/entity/work/data/341648136#Agent/kluwer_academic_plenum_publishers> ; # Kluwer Academic/Plenum Publishers
   schema:url <http://www.springerlink.com/openurl.asp?genre=book&isbn=978-0-306-46465-2> ;
   schema:url <http://site.ebrary.com/id/10053326> ;
   schema:url <http://www.myilibrary.com?id=20085> ;
   schema:url <http://link.library.utoronto.ca/eir/EIRdetail.cfm?Resources__ID=444081&T=F> ;
   schema:workExample <http://worldcat.org/isbn/9780306464652> ;
   wdrs:describedby <http://www.worldcat.org/title/-/oclc/123148269> ;
    .


Related Entities

<http://dbpedia.org/resource/New_York_City> # New York
    a schema:Place ;
   schema:name "New York" ;
    .

<http://experiment.worldcat.org/entity/work/data/341648136#Agent/kluwer_academic_plenum_publishers> # Kluwer Academic/Plenum Publishers
    a bgn:Agent ;
   schema:name "Kluwer Academic/Plenum Publishers" ;
    .

<http://experiment.worldcat.org/entity/work/data/341648136#Series/modern_inorganic_chemistry> # Modern inorganic chemistry.
    a bgn:PublicationSeries ;
   schema:hasPart <http://www.worldcat.org/oclc/123148269> ; # Metal dihydrogen and [sigma]-bond complexes
   schema:name "Modern inorganic chemistry." ;
   schema:name "Modern inorganic chemistry" ;
    .

<http://id.worldcat.org/fast/1017569> # Metal complexes
    a schema:Intangible ;
   schema:name "Metal complexes"@en ;
    .

<http://id.worldcat.org/fast/852856> # Chemical bonds
    a schema:Intangible ;
   schema:name "Chemical bonds"@en ;
    .

<http://id.worldcat.org/fast/964990> # Hydrogen
    a schema:Intangible ;
   schema:name "Hydrogen"@en ;
    .

<http://viaf.org/viaf/74067953> # Gregory J. Kubas
    a schema:Person ;
   schema:birthDate "1945" ;
   schema:familyName "Kubas" ;
   schema:givenName "Gregory J." ;
   schema:name "Gregory J. Kubas" ;
    .

<http://worldcat.org/isbn/9780306464652>
    a schema:ProductModel ;
   schema:isbn "0306464659" ;
   schema:isbn "9780306464652" ;
    .


Content-negotiable representations

Close Window

Please sign in to WorldCat 

Don't have an account? You can easily create a free account.