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    Migratory Insertion: Anionic Anionic

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    Mo Mobark
    The document discusses migratory insertion reactions, where a cisoidal anionic and neutral ligand on a metal complex couple together to form a new coordinated anionic ligand. Key features are that the oxidation state does not change, the ligands must be cisoidal, and a vacant site is generated. Common ligands that undergo this reaction are listed. Carbonyl and alkyl migrations are important for carbonylation reactions.

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    Migratory Insertion: Anionic Anionic

    Uploaded by

    Mo Mobark
    13 views3 pages
    The document discusses migratory insertion reactions, where a cisoidal anionic and neutral ligand on a metal complex couple together to form a new coordinated anionic ligand. Key features are that the oxidation state does not change, the ligands must be cisoidal, and a vacant site is generated. Common ligands that undergo this reaction are listed. Carbonyl and alkyl migrations are important for carbonylation reactions.

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    The document discusses migratory insertion reactions, where a cisoidal anionic and neutral ligand on a metal complex couple together to form a new coordinated anionic ligand. Key features are that the oxidation state does not change, the ligands must be cisoidal, and a vacant site is generated. Common ligands that undergo this reaction are listed. Carbonyl and alkyl migrations are important for carbonylation reactions.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    13 views3 pages

    Migratory Insertion: Anionic Anionic

    Uploaded by

    Mo Mobark
    The document discusses migratory insertion reactions, where a cisoidal anionic and neutral ligand on a metal complex couple together to form a new coordinated anionic ligand. Key features are that the oxidation state does not change, the ligands must be cisoidal, and a vacant site is generated. Common ligands that undergo this reaction are listed. Carbonyl and alkyl migrations are important for carbonylation reactions.

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    © All Rights Reserved
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    of 3

    Migratory Insertion/Elimination 1

    Migratory Insertion
    A migratory insertion reaction is when a cisoidal anionic and neutral
    ligand on a metal complex couple together to generate a new
    coordinated anionic ligand. This new anionic ligand is composed of the
    original neutral and anionic ligands now bonded to one another.
    General Features:
    1) No change in formal oxidation state (exception: alkylidenes)
    2) The two groups that react must be cisoidal to one another
    3) A vacant coordination site is generated by the migratory insertion.
    Therefore, a vacant site is required for the back elimination reaction (e.g.,
    -hydride elimination). A trapping ligand is often needed to coordinate to
    the empty site formed from a migratory insertion in order to stop the back
    elimination reaction.
    4) Migratory insertions are usually favored on more electron-deficient metal
    centers.

    migratory insertion ligand addition


    acyl
    O O CH3 O CH3
    C
    OC CO OC CO +L OC CO
    Mn Mn Mn
    OC CH3 OC OC L
    C C C
    O O O
    Mn(+1) Mn(+1) Mn(+1)
    18e- 16e- 18e-
    elimination

    The following are common anionic and neutral ligands that can do
    migratory insertion reactions with one another:
    Anionic: H, R (alkyl), Ar (aryl), acyl, O2 (oxo)
    Neutral: CO, alkenes, alkynes, carbenes
    Migratory Insertion/Elimination 2

    CO and alkyl migratory insertions (as shown above) are extremely


    important and are often generically referred to as carbonylation
    reactions. Hydride and CO migratory insertions to produce formyl
    groups are not common due to the thermodynamic instability of the
    formyl-metal interaction.

    Some Electronic effects


    R O Z
    R
    Z
    CO CO
    OC Fe +L OC Fe
    CO THF L
    C C
    O O
    best Lewis acid - can coordinate to electron-rich
    CO ligands and drain off some e- density

    Z+ = Li+ > Na+ > (Ph3)2N+

    strongest coordinating ligand - best trapping ligand

    L = PMe3 > PPhMe2 > PPh2Me > CO


    most electron-rich alkyl group makes the best nucleophile for
    migrating to the electron-deficient CO
    R = n-alkyl > PhCH2

    Note that the acyl ligand formed is not as good a donor compared to the
    starting alkyl. But the metal has gained (replaced) an electron
    withdrawing CO ligand with a better donating phosphine. Thus, the
    overall reaction with a trapping ligand is usually towards the migratory
    insertion.
    The reason that more electron-deficient metals favor CO-alkyl migratory
    insertions is that makes the carbon atom of the CO more electrophillic
    and susceptible to nucleophillic attack from the more electron-rich alkyl
    group.
    Migratory Insertion/Elimination 3

    Migration vs. Insertion


    There are two different “directions” that a migratory insertion can occur.
    A migration is when the anionic ligand moves and performs a
    nucleophillic-like intramolecular attack on the electrophillic neutral
    ligand. An insertion is when the neutral ligand moves and “inserts” into
    the bond between the metal and anionic ligand. Both of these pathways
    are illustrated below:
    Migration

    O O CH3
    C a MIGRATION rxn involves the
    OC CO OC CO anionic ligand doing a
    Mn Mn nucleophillic-like attack on the
    OC CH3 OC neutral ligand. This involves the
    C C anionic ligand moving to the site
    O O where the neutral ligand is
    coordinated. An empty
    Mn(+1) Mn(+1) coordination site is left behind.
    18e- 16e-
    Insertion
    O
    C an INSERTION rxn involves the
    OC CO OC CO neutral ligand moving over to
    Mn Mn O where the anionic ligand is
    OC CH3 OC coordinated and "inserting" into
    C C the anionic ligand-metal bond to
    CH3 generate the new anionic
    O O
    ligand. An empty coordination
    Mn(+1) Mn(+1) site is left behind from where
    18e- 16e- the neutral ligand originally was
    located.

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