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    7 - Carbene Carbyne Carbide Complexes

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    Nandini Gattadahalli
    This document discusses different types of carbenes, carbynes, and metal carbide complexes. It contrasts Fischer and Schrock carbene complexes, noting that Fischer complexes have electrophilic carbene carbons while Schrock complexes have nucleophilic carbene carbons. The key difference is whether the carbene ligand is viewed as neutral or dianionic. Similar contrasts are made between Fischer and Schrock carbyne complexes and how the carbyne ligand can be viewed as cationic, neutral, or anionic depending on the complex. Examples of synthesis routes for different carbene complexes are also provided.

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    7 - Carbene Carbyne Carbide Complexes

    Uploaded by

    Nandini Gattadahalli
    163 views8 pages
    This document discusses different types of carbenes, carbynes, and metal carbide complexes. It contrasts Fischer and Schrock carbene complexes, noting that Fischer complexes have electrophilic carbene carbons while Schrock complexes have nucleophilic carbene carbons. The key difference is whether the carbene ligand is viewed as neutral or dianionic. Similar contrasts are made between Fischer and Schrock carbyne complexes and how the carbyne ligand can be viewed as cationic, neutral, or anionic depending on the complex. Examples of synthesis routes for different carbene complexes are also provided.

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    7 - Carbene Carbyne Carbide Complexes (1)

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    This document discusses different types of carbenes, carbynes, and metal carbide complexes. It contrasts Fischer and Schrock carbene complexes, noting that Fischer complexes have electrophilic carbene carbons while Schrock complexes have nucleophilic carbene carbons. The key difference is whether the carbene ligand is viewed as neutral or dianionic. Similar contrasts are made between Fischer and Schrock carbyne complexes and how the carbyne ligand can be viewed as cationic, neutral, or anionic depending on the complex. Examples of synthesis routes for different carbene complexes are also provided.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    163 views8 pages

    7 - Carbene Carbyne Carbide Complexes

    Uploaded by

    Nandini Gattadahalli
    This document discusses different types of carbenes, carbynes, and metal carbide complexes. It contrasts Fischer and Schrock carbene complexes, noting that Fischer complexes have electrophilic carbene carbons while Schrock complexes have nucleophilic carbene carbons. The key difference is whether the carbene ligand is viewed as neutral or dianionic. Similar contrasts are made between Fischer and Schrock carbyne complexes and how the carbyne ligand can be viewed as cationic, neutral, or anionic depending on the complex. Examples of synthesis routes for different carbene complexes are also provided.

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    of 8

    Carbenes

    .
    : C . C
    - Stable Free Carbenes :
    Singlet Triplet
    CMe3

    F3C
    CMe3
    CF3 N
    Triplet
    :C :C :C .C.
    N Tomioka, JACS,
    P NiPr2 NiPr2 2003, 14664

    iPr2N

    Science, 2000, JACS, 2004, 8670


    288, 834

    Arduengo Carbene or CMe3


    Guy Bertrand
    NHC (N-Heterocyclic Carbene)
    Transition Metal Carbene Complexes
    FISCHER SCHROCK
    - Electrophilic Carbon - Nucleophilic Carbon

    :
    R R
    : :
    R R

    neutral CR2 (L-type ligand) CR22- (X2-type ligand)


    (similarities to PR3) (similarities to M=O or M=NR)
    properties strong -donor strong -donor
    poor or OK -acceptor strong -donor
    2-electron donor 4-electron donor

    R = -donor
    typical R groups in CR2 (OR, NR2, Ph) R = H, Alkyl

    Late TMs, Low oxidation Early TMs (often d0), High


    typical metals
    states (Mo0, Fe0 etc.) oxidation states (TaV, WVI)
    -acceptors Cl-, Cp-, Alkyl,
    typical co-ligands
    (CO, CNR, P(OR)3) Imido, Amido
    Transition Metal Carbene Complexes
    ▪ Carbenes (CR2) – these are not redox active ligands – i.e. Fischer or Schrock
    complexes have the same number of electrons. The difference is whether the
    carbene carbon is nucleophilic (Schrock) or electrophilic (Fischer).

    Fischer Carbene Schrock Carbene

    . .
    R - neutral triplet carbene
    M . . C - 2 covalent bonds Ligands viewed as
    X R - 2 electron donor being neutral 2e- donors

    M : C
    R

    - only one way to look at


    : - dianionic CR22-
    a Fischer carbene R - 2 bonds
    M :C Ligands not neutral
    - neutral singlet carbene R ( and  donation)
    - 1 donor covalent bond + - 4 electron donor
    weak -backdonation
    - 2 electron donor
    Transition Metal Carbene Complexes
    CO FISCHER

    N N
    OC CO Ar Ar
    Cr O C CH3
    OC Me Ta
    Cl
    - Examples : Ph Ru CHPh
    CH2
    CO
    Cl
    PCy3

    O Me
    SCHROCK
    M C
    Ph

    - Exceptions :

    If Schock If Fischer TaV = d0


    WVI = d0 WIV = d2 2 x Cp- = 12
    2 x Cp- = 12 2 x Cp- = 12 CH3 CH3
    W Ta Me- = 2
    Me- = 2 Me- = 2 CH2 CH2 CH22- = 4
    CH22- = 4 neutral CH2 = 2 Total = 18
    Total = 18 Total = 18

    FISCHER !!! SCHROCK


    Synthesis of Carbene Complexes
    Acyl or Iminoacyl Complex + Electrophile :

    O O
    Me- Me I
    M CO M C M C

    [Pt(C NMe)4]2+ + 4 MeNH2 [Pt{C(NHMe)2}4]2+

    From alkyls with -hydrogens

    Base M C R
    R
    H - H+
    M R
    R - H-
    Lewis acid M C R
    (e.g. BAr3 or CPh3+) R

    Using a carbene source (e.g. a diazoalkane, R2C=N=N)

    LxM + CH2N2 LxM=CH2 + N2


    Metal Carbyne Complexes
    - Also Fischer and Schrock bonding extremes, but the distinction is less
    marked → considerable ambiguity in many cases.

    FISCHER SCHROCK
    Br2
    Br(OC)4W CR (dme)Br3W CR
    dme
    d4 dme = 1,2-dimethoxyethane d0
    :

    :
    : R : R

    :
    CR- = an LX-type ligand CR3- = an X3-type ligand
    (similarities with N3- and C4-)

    1 x -donor 1 x -donor
    1 x -donor 2 x -donor
    1 x -acceptor
    Metal Carbyne Complexes
    Fischer Carbyne Schrock Carbyne
    ▪ Carbynes (CR) are not redox active ligands
    M : C R

    Ligand cationic
    - cationic CR+ (2 e- donor)
    - 1 donor covalent bond +
    2 vacant p-orbitals for M-->L
    -backdonation

    . .
    M : C R . C R Ligands viewed as
    M .
    being neutral 3e- donors

    - neutral doublet CR (3 e- donor) - neutral quartet CR (3 e- donor) - useful for electron counting
    - 2 covalent bonds + - 3 covalent bonds if you don't know if a CR2
    1 vacant p-orbital for M-->L ligand is a Fischer or
    -backdonation Schrock carbene.

    :
    :

    Ligands anionic
    M : C R M : : C R
    - Better method for working
    out the formal oxidation
    - anionic CR- (4 e- donor) - trianionic CR3- (6 e- donor) state of a metal coordinated
    - 2 donor covalent bonds + - 3 donor covalent bonds to a CR2 ligand. Using this method,
    1 vacant p-orbital for Schrock carbynes are almost
    M-->L -backdonation always found with d0-metals
    Metal Carbide Complexes

    C. C. Cummins et al.,
    Chem. Commun., 1997, 1995

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