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    3 - Overview

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    Agita Raka
    This document provides an overview of organometallic chemistry. It discusses the differences between organic and organometallic chemistry, including the more ionic nature of metal-ligand bonds in organometallics. The focus of organometallic chemistry is understanding and tuning reactivity through analyzing reaction mechanisms. Main factors that influence structure and reactivity include metal-carbon bond strengths, electronegativity, electron counts, and sterics. Common reaction types are also outlined, such as oxidative addition/reductive elimination and insertion/elimination. Characterization techniques discussed include X-ray crystallography, NMR, and computational methods.

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    3 - Overview

    Uploaded by

    Agita Raka
    68 views28 pages
    This document provides an overview of organometallic chemistry. It discusses the differences between organic and organometallic chemistry, including the more ionic nature of metal-ligand bonds in organometallics. The focus of organometallic chemistry is understanding and tuning reactivity through analyzing reaction mechanisms. Main factors that influence structure and reactivity include metal-carbon bond strengths, electronegativity, electron counts, and sterics. Common reaction types are also outlined, such as oxidative addition/reductive elimination and insertion/elimination. Characterization techniques discussed include X-ray crystallography, NMR, and computational methods.

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    This document provides an overview of organometallic chemistry. It discusses the differences between organic and organometallic chemistry, including the more ionic nature of metal-ligand bonds in organometallics. The focus of organometallic chemistry is understanding and tuning reactivity through analyzing reaction mechanisms. Main factors that influence structure and reactivity include metal-carbon bond strengths, electronegativity, electron counts, and sterics. Common reaction types are also outlined, such as oxidative addition/reductive elimination and insertion/elimination. Characterization techniques discussed include X-ray crystallography, NMR, and computational methods.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    68 views28 pages

    3 - Overview

    Uploaded by

    Agita Raka
    This document provides an overview of organometallic chemistry. It discusses the differences between organic and organometallic chemistry, including the more ionic nature of metal-ligand bonds in organometallics. The focus of organometallic chemistry is understanding and tuning reactivity through analyzing reaction mechanisms. Main factors that influence structure and reactivity include metal-carbon bond strengths, electronegativity, electron counts, and sterics. Common reaction types are also outlined, such as oxidative addition/reductive elimination and insertion/elimination. Characterization techniques discussed include X-ray crystallography, NMR, and computational methods.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 28

    Organometallic Chemistry

    an overview reactions

    Peter H.M. Budzelaar

    Between organic and inorganic...


    Organic chemistry: more or less covalent C-X bonds rigid element environments fixed oxidation states (better: valencies)

    ??Organometallic chemistry??
    Inorganic chemistry: primarily ionic M-X bonds, dative M-L bonds variable and often fluxional environments variable oxidation states

    Overview of Organometallic Chemistry

    Organometallic reactivity
    Since most organometallics are intermediates, the focus in organometallic chemistry is usually on understanding and tuning reactivity This starts with analyzing reaction mechanisms in terms of elementary steps The number of possible elementary steps is larger than in "pure organic" chemistry, but the ideas are similar

    Overview of Organometallic Chemistry

    Organometallic structures
    Knowledge of inorganic and coordination chemistry is useful to understand geometries, electron counts and oxidation states of organometallic compounds Organometallics are more covalent and often less symmetric than coordination compounds, so orbital symmetry arguments are not as important

    Overview of Organometallic Chemistry

    Trends in organometallic chemistry


    Organometallic chemistry is concerned with all metals, in combination with all "organic" elements.
    there are many metals !

    Generalization is important
    the chemistry of e.g. Fe is not much more complicated than that of C, but after that there are 80 more metals... we divide reactions in broader categories than organic chemists do

    We concentrate on the M side of the M-C bond, and on how to tune its reactivity

    Overview of Organometallic Chemistry

    Elements of interest
    Organic elements Main group metals Transition metals

    Overview of Organometallic Chemistry

    Organic vs organometallic reactivity


    Organic chemistry:
    C-C / C-H : nearly covalent Cd+-Xd- : polar (partly ionic) reactivity dominated by nucleophilic attack at C SN2 and SN1 like reactivity
    -X X SN1 int (6-e) X Y -X Y SN2 TS (10-e ?) Y Y

    Organometallic chemistry:
    C is the negative end of the M-C bond ("umpolung") reactivity dominated by electrophilic attack at C or nucleophilic attack at M associative and dissociative substitution at M - C2H4

    dissociative (C2H4)PdCl2

    CO (C2H4)(CO)PdCl2 - C2H4

    (C2H4)2PdCl2 CO

    ?
    (C2H4)2(CO)PdCl2 associative

    Overview of Organometallic Chemistry

    Main-group organometallics
    s and p orbitals.
    Me Al Me Me Al Me Me Me

    8-e rule, usually. with a lot of exceptions

    8-e

    Cl

    10-e

    Cl Sn Me Me More electropositive and larger: O higher coordination numbers, N regardless of the number of electrons.

    Early" groups and not very electropositive: lower coordination numbers. Me Zn Me


    4-e
    8
    Overview of Organometallic Chemistry

    Main-group organometallics

    Metal is the "d+" side of the M-C bond. Chemistry dominated by nucleophilic attack of Cd- at electrophiles.
    this is also the main application in organic synthesis

    MeMgBr + Me2CO

    Me3COMgBr

    note: this is a simplified picture of the Grignard reaction

    Overview of Organometallic Chemistry

    Main-group organometallics
    M-M multiple bonds are fairly weak and rather reactive
    they are a curiosity and relatively unimportant, certainly compared to C-C multiple bonds

    Bond strengths in kcal/mol: C-C 85 C=C 150 N-N 40 N=N 100 P-P 50 P=P 75 Multiple-bonded compounds often have unusual geometries

    "Me4Sn2"

    Me4C2

    10

    Overview of Organometallic Chemistry

    Transition-metal organometallics
    s, p and d orbitals 18-e rule, sometimes 16-e
    other counts relatively rare

    Ni

    CO OC OC Cr CO CO CO
    Fe

    18-e 18-e
    Et3P Et3P Pt Me Cl

    18-e

    16-e

    11

    Overview of Organometallic Chemistry

    Transition-metal organometallics
    Lower electron counts if metals are sterically saturated:
    nor Co nor nor = nor nor

    Me Me Me Me W Me Me

    12-e

    13-e
    Ti Me Me

    16-e
    12
    Overview of Organometallic Chemistry

    Transition-metal organometallics
    Often ligands capable of donating 2-8 electrons
    Preference for p-system ligands (good overlap with d-orbitals)

    olefin

    O C

    carbene C

    cyclopentadienyl allyl

    2e

    2e

    2e

    3e

    5e

    Bonding to neutral ligands (olefin/diene/CO/phosphine) relatively weak


    Important for catalysis!

    13

    Overview of Organometallic Chemistry

    Transition-metal organometallics
    An olefin complex: (Acac)Ir(NCMe)(C2H4)

    donation

    backdonation
    14
    Overview of Organometallic Chemistry

    Transition-metal organometallics
    Forbidden reactions ?
    + ?

    Mo

    Mo

    No symmetry Very fast

    Symmetry-forbidden Does not happen

    15

    Overview of Organometallic Chemistry

    Reactivity of the M-C bond


    Polar reactive towards e.g. Water:
    M-OH + H-C

    Me3Al explodes with water; Me4Sn does not react.

    Oxygen:

    M-O-O-C

    Me2Zn inflames in air; Me4Ge does not react.

    Carbonyl groups:

    M-O-C C

    MeLi adds at -80C, Me3Sb not even at +50C.

    16

    Overview of Organometallic Chemistry

    Reactivity of the M-C bond


    Oxidation and hydrolysis: large driving force Bond strengths in kcal/mol: Al-C 65 As-C 55 Al-O 119 As-O 72 Al-Cl 100

    Si-C 74 Si-O 108 Si-Cl 91

    17

    Overview of Organometallic Chemistry

    Organometallic reaction steps


    Ligand dissociation / coordination

    Me3Al + NMe3 6e

    Me3Al-NMe3 8e

    note: free Me3Al dimerizes to Me6Al2

    Mo(CO)6 18e
    18

    Mo(CO)5 + CO 16e
    Overview of Organometallic Chemistry

    Organometallic reaction steps


    Insertion and b-elimination
    MeMgBr + MeC N Me2C=NMgBr

    N N Fe Me N

    N N Fe Me N

    N Fe N

    N Me

    N N Fe Me = N N Ar = N Ar Fe N Ar

    19

    Overview of Organometallic Chemistry

    Organometallic reaction steps


    Insertion and b-elimination
    P Pd P P Pd H P

    H
    P P = Ph2P PPh2

    20

    Overview of Organometallic Chemistry

    Organometallic reaction steps


    Oxidative addition / Reductive elimination
    P P Rh Cl P H2 P P H Rh Cl H P "P" = PPh3

    21

    Overview of Organometallic Chemistry

    Organometallic reaction steps


    Oxidative addition / Reductive elimination
    Me O O Rh L L MeI O Rh L I L O I Rh O Me L L = PPh3 L L = P(OPh)3

    22

    Overview of Organometallic Chemistry

    Organometallic reaction steps


    s-bond metathesis
    Lu CH3 *CH4 H3 *C H Lu C H3

    Lu

    *CH3

    14 e

    23

    Overview of Organometallic Chemistry

    Organometallic reaction steps

    Redox reactions

    Fe

    - e-

    Fe

    Homolysis
    Et Hg Et Et Hg + Et

    24

    Overview of Organometallic Chemistry

    Organometallic reaction steps


    Reactivity of coordinated ligands

    25

    Overview of Organometallic Chemistry

    Factors governing structure and reactivity of organometallic compounds


    M-C, M-X bond strengths Electronegativity of M (polarity of M-C etc bonds) Number of (d) electrons Coordination number Steric hindrance

    26

    Overview of Organometallic Chemistry

    Trends in the periodic table


    Main group metals: left and down: more electropositive down: higher oxidation states less stable Transition metals: middle: strongest preference for 18-e 2nd and 3rd row: strong preference for paired electrons (low-spin states) down: higher oxidation states more stable

    27

    Overview of Organometallic Chemistry

    Working with organometallics


    Synthesis and reactivity studies (inert atmosphere!): Glove box Schlenk line, specialized glassware Characterization: Xray diffraction structure bonding NMR structure en dynamic behaviour (calculations) IR MS EPR Not: GC LC

    28

    Overview of Organometallic Chemistry

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