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    Labile or Inert?

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    veronica
    The document discusses factors that determine whether a metal complex is labile or inert, including: 1. The size, charge, and number of d-electrons of the metal ion. Smaller, higher charged ions with fewer d-electrons tend to be more inert. 2. The d-electron configuration, which affects reactivity - d4 high spin and d7-d9 complexes tend to be more labile. It also discusses the trans-influence and trans-effect of ligands. Ligands with stronger sigma-donating abilities have a larger trans-influence, weakening metal-leaving group bonds. The trans-effect considers both this influence and stabilization of intermediates, with

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    Labile or Inert?

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    veronica
    78 views7 pages
    The document discusses factors that determine whether a metal complex is labile or inert, including: 1. The size, charge, and number of d-electrons of the metal ion. Smaller, higher charged ions with fewer d-electrons tend to be more inert. 2. The d-electron configuration, which affects reactivity - d4 high spin and d7-d9 complexes tend to be more labile. It also discusses the trans-influence and trans-effect of ligands. Ligands with stronger sigma-donating abilities have a larger trans-influence, weakening metal-leaving group bonds. The trans-effect considers both this influence and stabilization of intermediates, with

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    2019-04-29 Guest Lecture - T. Powers

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    The document discusses factors that determine whether a metal complex is labile or inert, including: 1. The size, charge, and number of d-electrons of the metal ion. Smaller, higher charged ions with fewer d-electrons tend to be more inert. 2. The d-electron configuration, which affects reactivity - d4 high spin and d7-d9 complexes tend to be more labile. It also discusses the trans-influence and trans-effect of ligands. Ligands with stronger sigma-donating abilities have a larger trans-influence, weakening metal-leaving group bonds. The trans-effect considers both this influence and stabilization of intermediates, with

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    78 views7 pages

    Labile or Inert?

    Uploaded by

    veronica
    The document discusses factors that determine whether a metal complex is labile or inert, including: 1. The size, charge, and number of d-electrons of the metal ion. Smaller, higher charged ions with fewer d-electrons tend to be more inert. 2. The d-electron configuration, which affects reactivity - d4 high spin and d7-d9 complexes tend to be more labile. It also discusses the trans-influence and trans-effect of ligands. Ligands with stronger sigma-donating abilities have a larger trans-influence, weakening metal-leaving group bonds. The trans-effect considers both this influence and stabilization of intermediates, with

    Copyright:

    © All Rights Reserved
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    Download as pdf or txt
    of 7

    Labile or inert?

    Labile – a compound that undergoes reactions with a relatively high rate of


    substitution
    Inert – a compound that undergoes reactions with a slow rate of substitution
    Inert is a relative term, t1/2 > 1 min at 25 oC

    3 main factors that affect the whether a complex is labile or inert:

    1. Size: Smaller metal ions tend to be more inert as ligands are held more
    tightly.
    2. Charge on Metal: The greater the charge on a metal ion in a complex,
    the greater the tendency towards the complex being inert
    3. Number of d electrons and configuration
    Octahedral geometry d-electron configuration: labile or inert?
    # of d-electrons /
    Reactivity Notes
    configuration
    d1 Labile N/A
    d2 Labile N/A
    d3 Inert N/A
    d4 Low Spin Inert N/A
    d4 High Spin Labile Especially labile as it is structurally distorted by the Jahn-Teller effect.
    d5 Low Spin Inert N/A
    d5 High Spin Labile N/A
    d6 Low Spin Inert N/A
    d6 High Spin Labile N/A
    d7 High Spin Labile N/A
    d8 Square Planar Inert For d8 and above low spin is the same as high spin.
    d8 Intermediate This configuration is intermediate, especially with weak field ligands.
    Like d4 H.S. this configuration is especially labile as it is distorted by
    d9 Labile
    Jahn-Teller effect.
    d10 Labile N/A
    Trans-effect vs Trans-influence
    Trans-influence – If “A” forms a very strong sigma-bond to the metal, it competes for the
    metal orbitals with the leaving group, “X,” thus weakening the M–X bond

    Trans-influence determined by sigma-donor strength (basicity):

    R3Si – > H – > H3C – , NC – > olefin, CO > R3P > NO2– > I – > Br – > Cl – > H3N > HO – > H2O

    Trans-effect – A strongly sigma-donating and/or pi-accepting group “A” will greatly


    increase the reaction rate relative to a weak sigma-donor/poor pi-acid “A.” Factors that
    dominate the trans-effect include:
    1. Ground state weakening of M–X bond (trans-influence)
    2. Stabilization of the presumed 5-coordinate intermediate

    Taking into account BOTH trans-influence and pi- effects:

    NO+ > CO > CN – > PR3, H – > H3C – > Ph – > NO2 –, I – > Br – > Cl – > py, H2O, HO –, NH3
    Inner Sphere Reactivity
    Metal Centered – gain or loss of ligands
    1. Ligand substitution
    2. Oxidative addition
    3. Reductive elimination
    4. Nucleophilic displacement
    5. Transmetallation

    Ligand Centered – modification of ligands


    1. Migratory insertion
    a) Carbonyl insertion
    b) 1,2–insertion
    2. Hydride elimination
    3. Abstraction
    Monsanto Acetic Acid Process
    Olefin hydroformylation
    At each step give:
    1. Type of reaction
    2. Oxidation state
    3. d-electron count
    4. Total electron count
    Chauvin mechanism for olefin metathesis

    At each step give type


    of reaction

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