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    Chem 589: Organometallic Chemistry Bonding To Catalysis

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    EnesEmreTaş
    Organometallic compounds contain metal-carbon bonds. There are three main types of bonding patterns: [1] ionic compounds with electropositive metals, [2] two-electron covalent bonds with less electropositive metals, and [3] non-classical multi-center bonds. Common preparation methods include oxidative addition, metal exchange, metathesis, and carbometallation reactions. Organolithium compounds specifically exhibit oligomerization and form multi-center bonds depending on conditions like temperature and solvent.

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    Chem 589: Organometallic Chemistry Bonding To Catalysis

    Uploaded by

    EnesEmreTaş
    82 views20 pages
    Organometallic compounds contain metal-carbon bonds. There are three main types of bonding patterns: [1] ionic compounds with electropositive metals, [2] two-electron covalent bonds with less electropositive metals, and [3] non-classical multi-center bonds. Common preparation methods include oxidative addition, metal exchange, metathesis, and carbometallation reactions. Organolithium compounds specifically exhibit oligomerization and form multi-center bonds depending on conditions like temperature and solvent.

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    Organometallic Chemistry

    Original Title

    Organometalic

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    Organometallic compounds contain metal-carbon bonds. There are three main types of bonding patterns: [1] ionic compounds with electropositive metals, [2] two-electron covalent bonds with less electropositive metals, and [3] non-classical multi-center bonds. Common preparation methods include oxidative addition, metal exchange, metathesis, and carbometallation reactions. Organolithium compounds specifically exhibit oligomerization and form multi-center bonds depending on conditions like temperature and solvent.

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    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    82 views20 pages

    Chem 589: Organometallic Chemistry Bonding To Catalysis

    Uploaded by

    EnesEmreTaş
    Organometallic compounds contain metal-carbon bonds. There are three main types of bonding patterns: [1] ionic compounds with electropositive metals, [2] two-electron covalent bonds with less electropositive metals, and [3] non-classical multi-center bonds. Common preparation methods include oxidative addition, metal exchange, metathesis, and carbometallation reactions. Organolithium compounds specifically exhibit oligomerization and form multi-center bonds depending on conditions like temperature and solvent.

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    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
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    Chem 589

    Organometallic Chemistry
    Bonding to Catalysis
    Organometallic Compounds
    Original definition: are those in which C atoms of
    organic groups are bound to metals or elements such
    as B, P and Si.
    Now: Metals can be bound to atoms other than C of
    the organic groups
    What type of bonding patterns are seen in organometallic compounds?

    a) Ionic compounds of electropositive metals such as Na, K and Ca.


    Na acetylide

    b) s bonded compounds bound to a metal by 2 electron covalent bond


    seen in less electropositive metals and nonmetallic elements

    c) Non-classically bonded compounds where 2 electron -3 center or 2 electron- 4 center


    bonds are formed. Methyl Lithium
    Ferrocene

    1952
    1760 Cadet

    1836

    + HCl Zn
    .

    tetramethyldiarsane
    1849 Edward Frankland
    Chemistry of Organometallic Compounds

    Main group organometallic The group of the metal or metalloid


    compounds

    The nature of the ligand


    Organotransition metal
    compounds
    M-C Bond Stability

    M d (pm) r= d-rC
    d=M-C bond length
    r= covalent radius of M
    Be 179 102
    rC= covalent radius of C
    rC= 77 pm
    Mg 219 142

    Zn 196 119

    Cd 211 134

    Hg 210 133
    M d (pm) r= d-rC M d (pm) r= d-rC

    B 156 79 N 157 70

    Al 197 120 P 187 110

    Ga 198 121 As 196 119

    In 223 146 Sb 212 135

    Tl 225 148 Bi 226 149

    C 154 77

    Si 188 111

    Ge 195 118

    Sn 217 140

    Pb 224 147
    M D (M-C) Bond energy kJ/mol
    Zn 177
    Cd 139
    MMe2
    Hg 121

    B 365 B-O 526 B-Cl 456


    Al 274 Al-O 500 Al-Cl 420
    MMe3 Ga 247
    In 160

    C 358
    Si 311 Si-O 452 Si-Cl 381 Si-F 565
    MMe4 Ge 249
    Sn 217 Sn-Cl 323
    Pb 152
    Preparation Methods

    A. Oxidative Addition Direct synthesis 1

    Transmetallation 2

    Metal Exchange 3

    B. Exchange Metathesis 4

    Metal-Halogen Exchange 5

    Metalation 6

    Mercuration 7
    Hydrometallation 8

    C. Insertion Carbometallation 9

    Carbene Insertion 10

    Decarboxylation 11
    D. Elimination

    Arylation via Diazonium Salts 12


    Reaction Patterns

    Reactions of organometallic compounds of electropositive elements are determined by

    -Carbanion character of the organic moiety

    -Presence or absence of a potential coordination site on the central metal atom


    Organolithium Compounds
    Molecular Association : Forming oligomers in solid state and in solution
    Methyl Lithium CH3Li

    4center -2 electron bonds


    d(Li-C ) 231 pm
    d(Li-C ) 236 pm
    d(Li-Li) 268 pm
    LiR Solvent Aggregation

    LiCH3 Hydrocarbon Hexamer (Li6 octahedron)

    THF, Et2O Tetramer (Li4 tetrahedron)

    Me2NCH2CH2NMe2 Monomer
    (TMEDA)
    Cyclohexane Hexamer
    Li(nBu)
    Et2O Tetramer

    Li(t-Bu) Hydrocarbon Tetramer

    THF, Et2O Dimer


    Li (C6H5)
    Monomer
    Li(CH2C6H5) THF, Et2O

    Li(C3H5) Et2O Highly aggregated n>10


    THF Monomer
    Temperature /solvent combinations for alkyl lithium compounds having halflives
    more than 100 hrs
    0C Et2O THF Dimethoxyethane (DME)

    +50 LiCH3

    +25 Li (C6H5)

    0 Li(nBu) LiCH3

    -25 Li sec(Bu) Li (C6H5) LiCH3

    -25

    -75 Li sec(Bu)

    -100 Li(t-Bu) Li(nBu)

    -150 Li(t-Bu)
    C-H acidity in nonaqueous media R’H
    Compound pKa
    (CN)3C-H -5
    21
    H2SO4 -2

    (NO2)3C-H 0
    24
    HClO3 0
    30
    CH3COOH 4.7
    35
    HCN 9.4

    O2NCH3 10

    37
    15

    n-Bu-H 44

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