ACS Publications. Most Trusted. Most Cited. Most Read
Valence Bond Approach of Metal−Ligand Bonding in the Dewar−Chatt−Duncanson Model
My Activity

Figure 1Loading Img
    Article

    Valence Bond Approach of Metal−Ligand Bonding in the Dewar−Chatt−Duncanson Model
    Click to copy article linkArticle link copied!

    View Author Information
    UMR 6180 - Chirotechnologies:  Catalyse et Biocatalyse, CNRS/Université Paul Cézanne (Aix-Marseille III), Campus St Jérôme Case A 62, 13397 Marseille Cedex 20, France, Laboratoire de Chimie Théorique − UMR 7616 CNRS/Université Pierre et Marie Curie, “Le Raphaël”, 3 rue Galilée, 94200 Ivry-Sur-Seine CEDEX, France
    Other Access OptionsSupporting Information (1)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2007, 46, 26, 11390–11396
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic701434e
    Published November 29, 2007
    Copyright © 2007 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Metal−ligand bonding, as considered in the Dewar−Chatt−Duncanson model, is described via an ab initio Valence Bond (VB) approach and applied to typical Pd−L complexes (L = NH3, PH3, CH2, SiH2). A progressive construction of the VB wave function is followed and leads to a very compact, though accurate, description of metal−ligand bonds. A description with the donation interaction only (ligand−metal) is first constructed and enriched so the back-donation interactions (metal−ligand) are also introduced. This latter VB wave function, although being extremely compact, provides bonding energies in agreement with standard (correlated) methods. A comparison between the two VB levels allows a quantification of adiabatic back-bonding energies and reveals very different trends between the ligands considered. A very faint back-donation in Pd−NH3 is found, which contrasts with a significant effect in Pd−PH3. Back-donation is, however, more important in Pd−XH2 complexes. In Pd−CH2, it is such that it even represents the major source of bonding. For Pd−SiH2, back-donation is slightly weaker than donation. The nature of the interaction in these metal−ligand complexes is revealed by the VB wave function analysis. Results are as well rationalized using the simple molecular orbital picture and compared to previous studies.

    Copyright © 2007 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

     CNRS/Université Paul Cézanne (Aix-Marseille III).

    *

     To whom correspondence should be addressed. E-mail:  braida@ lct.jussieu.fr (B.B.), [email protected] (S.H.).

     CNRS/Université Pierre et Marie Curie.

    Supporting Information Available

    Click to copy section linkSection link copied!

    Coordinates and absolute energies for all of computed structures at all of the levels. This material is available free of charge via the Internet at http:// pubs.acs.org.

    Terms & Conditions

    Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai

    This article is cited by 19 publications.

    1. Hongling Yang, Xiaoxu Wang, Qinggang Liu, Aijian Huang, Xun Zhang, Yi Yu, Zewen Zhuang, Ganggang Li, Yang Li, Qing Peng, Xin Chen, Hai Xiao, Chen Chen. Heterogeneous Iridium Single-Atom Molecular-like Catalysis for Epoxidation of Ethylene. Journal of the American Chemical Society 2023, 145 (12) , 6658-6670. https://doi.org/10.1021/jacs.2c11380
    2. Miguel Reina, Itzel Guerrero-Ríos, Antonio Reina. The Study of Metal–Carbonyl Complexes by Means of Computational IR Spectra Analysis: A Remote Didactic Approach Based on Chemical Thinking. Journal of Chemical Education 2022, 99 (9) , 3211-3217. https://doi.org/10.1021/acs.jchemed.2c00577
    3. Dajiang Huang, Fuming Ying, Sifeng Chen, Chen Zhou, Peifeng Su, Wei Wu. Metal–Ligand Bonds in Rare Earth Metal–Biphenyl Complexes. Inorganic Chemistry 2022, 61 (21) , 8135-8143. https://doi.org/10.1021/acs.inorgchem.2c00144
    4. Patrick Federmann, Tim Richter, Hubert Wadepohl, Joachim Ballmann. Synthesis and Reactivity of [PCCP]-Coordinated Group 5 Alkyl and Alkylidene Complexes Featuring a Metallacyclopropene Backbone. Organometallics 2019, 38 (21) , 4307-4318. https://doi.org/10.1021/acs.organomet.9b00577
    5. Zhi-Feng Li, Yanzhong Fan, Nathan J. DeYonker, Xiting Zhang, Cheng-Yong Su, Huiying Xu, Xianyan Xu, and Cunyuan Zhao . Platinum(II)-Catalyzed Cyclization Sequence of Aryl Alkynes via C(sp3)–H Activation: A DFT Study. The Journal of Organic Chemistry 2012, 77 (14) , 6076-6086. https://doi.org/10.1021/jo300849t
    6. Yannick Carissan, Denis Hagebaum-Reignier, Nicolas Goudard and Stéphane Humbel . Hückel-Lewis Projection Method: A “Weights Watcher” for Mesomeric Structures. The Journal of Physical Chemistry A 2008, 112 (50) , 13256-13262. https://doi.org/10.1021/jp803813e
    7. Jean-Marie Ducéré, Christine Lepetit, Bernard Silvi and Remi Chauvin. Quantifying the Donor−Acceptor Properties of Carbon Monoxide and Its Carbo-mer Using ELF Analysis. Organometallics 2008, 27 (20) , 5263-5272. https://doi.org/10.1021/om800578c
    8. Enhua Zhang, Hajime Hirao. Synergistic Charge Transfer Effect in Ferrous Heme–CO Bonding within Cytochrome P450. Molecules 2024, 29 (4) , 873. https://doi.org/10.3390/molecules29040873
    9. Yannick Carissan, Denis Hagebaum-Reignier, Nicolas Goudard, Hind Benzidi, Stéphane Humbel. Local Description with Lewis Structures at the Hückel Level. 2024, 605-616. https://doi.org/10.1016/B978-0-12-821978-2.00036-2
    10. Prativa Behera, Lisa Roy. Transition metals and their complexes as homogeneous catalysts. 2024, 63-91. https://doi.org/10.1016/B978-0-443-15181-1.00011-0
    11. Tatsuhiro Murakami, Naoki Matsumoto, Takashi Fujihara, Toshiyuki Takayanagi. Possible Roles of Transition Metal Cations in the Formation of Interstellar Benzene via Catalytic Acetylene Cyclotrimerization. Molecules 2023, 28 (21) , 7454. https://doi.org/10.3390/molecules28217454
    12. Samira Gholami, Mohammad Aarabi, Sławomir J. Grabowski. Proton and Lithium Cations Linked to π‐Electron and σ‐Electron Systems: Are Such Interactions beyond or within the Definition of Hydrogen/Lithium Bond?. ChemPhysChem 2022, 23 (20) https://doi.org/10.1002/cphc.202200273
    13. Shizhu Song, Qi Li, Lifang Zhang, Yanqing Wang, Xiaojuan Liu. Imidazolium ionic Liquid-Regulated Sub-5-nm Pt(1 1 1) with a stable configuration anchored on hollow carbon nanoshells for efficient oxygen reduction. Journal of Colloid and Interface Science 2022, 606 , 177-191. https://doi.org/10.1016/j.jcis.2021.08.010
    14. Slađana Đorđević, Slavko Radenković, Sason Shaik, Benoît Braïda. On the Nature of the Bonding in Coinage Metal Halides. Molecules 2022, 27 (2) , 490. https://doi.org/10.3390/molecules27020490
    15. Benoit de Courcy, Etienne Derat, Jean‐Philip Piquemal. Bridging organometallics and quantum chemical topology: Understanding electronic relocalisation during palladium‐catalyzed reductive elimination. Journal of Computational Chemistry 2015, 36 (15) , 1167-1175. https://doi.org/10.1002/jcc.23911
    16. John Morrison Galbraith, Andrew M. James, Coleen T. Nemes. The effect of diffuse basis functions on valence bond structural weights. Molecular Physics 2014, 112 (5-6) , 654-660. https://doi.org/10.1080/00268976.2013.850179
    17. Etienne Derat, Giovanni Maestri. Understanding palladium complexes structures and reactivities: beyond classical point of view. WIREs Computational Molecular Science 2013, 3 (6) , 529-541. https://doi.org/10.1002/wcms.1137
    18. Hui Li, Qingzhong Li, Ran Li, Wenzuo Li, Jianbo Cheng. Prediction and characterization of HCCH⋅⋅⋅AuX (X = OH, F, Cl, Br, CH3, CCH, CN, and NC) complexes: A π Au-bond. The Journal of Chemical Physics 2011, 135 (7) https://doi.org/10.1063/1.3626142
    19. James W. Herndon. The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the Year 2007. Coordination Chemistry Reviews 2009, 253 (9-10) , 1517-1595. https://doi.org/10.1016/j.ccr.2008.12.013

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2007, 46, 26, 11390–11396
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic701434e
    Published November 29, 2007
    Copyright © 2007 American Chemical Society

    Article Views

    985

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.