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    11 - TransitionMetal

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    tuyenvip441999
    The document discusses organometallic complexes of transition metals. It describes how the properties of transition metal complexes vary depending on their location in the periodic table. Early transition metals form more reactive complexes with polar metal-carbon bonds, while late transition metals form more stable complexes with weaker metal-carbon bonds. Middle transition metals commonly form 18-electron complexes with strongly-bound ligands. The document outlines common ligands like carbon monoxide and phosphines that act as both sigma donors and pi acceptors. It also discusses the synthesis, reactivity, and decomposition pathways of various metal alkyl, aryl, and hydride complexes.

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    11 - TransitionMetal

    Uploaded by

    tuyenvip441999
    53 views37 pages
    The document discusses organometallic complexes of transition metals. It describes how the properties of transition metal complexes vary depending on their location in the periodic table. Early transition metals form more reactive complexes with polar metal-carbon bonds, while late transition metals form more stable complexes with weaker metal-carbon bonds. Middle transition metals commonly form 18-electron complexes with strongly-bound ligands. The document outlines common ligands like carbon monoxide and phosphines that act as both sigma donors and pi acceptors. It also discusses the synthesis, reactivity, and decomposition pathways of various metal alkyl, aryl, and hydride complexes.

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    TransitionMetal

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    The document discusses organometallic complexes of transition metals. It describes how the properties of transition metal complexes vary depending on their location in the periodic table. Early transition metals form more reactive complexes with polar metal-carbon bonds, while late transition metals form more stable complexes with weaker metal-carbon bonds. Middle transition metals commonly form 18-electron complexes with strongly-bound ligands. The document outlines common ligands like carbon monoxide and phosphines that act as both sigma donors and pi acceptors. It also discusses the synthesis, reactivity, and decomposition pathways of various metal alkyl, aryl, and hydride complexes.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    53 views37 pages

    11 - TransitionMetal

    Uploaded by

    tuyenvip441999
    The document discusses organometallic complexes of transition metals. It describes how the properties of transition metal complexes vary depending on their location in the periodic table. Early transition metals form more reactive complexes with polar metal-carbon bonds, while late transition metals form more stable complexes with weaker metal-carbon bonds. Middle transition metals commonly form 18-electron complexes with strongly-bound ligands. The document outlines common ligands like carbon monoxide and phosphines that act as both sigma donors and pi acceptors. It also discusses the synthesis, reactivity, and decomposition pathways of various metal alkyl, aryl, and hydride complexes.

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    At a glance
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    The document discusses the properties and reactivity of transition metal organometallics.

    Early transition metals are strongly electrophilic and oxophilic, have few d-electrons, and prefer hard donors like nitrogen and oxygen.

    Middle transition metals have many accessible oxidation states, are mostly 18 electron complexes, and prefer sigma donor/pi acceptor ligands like carbon monoxide.

    Transition-metal

    Organometallics

    Peter H.M. Budzelaar

    Transition metals are never on time


    Late

    Early
    Middle

    Transition-metal Organometallics

    Early Transition Metals


    Groups 3,4

    Strongly electrophilic and oxophilic


    Few redox reactions (exception: Ti)
    Nearly always < 18e
    Polar and very reactive M-C bonds
    (to alkyl and aryl)

    Few d-electrons:
    preference for "hard" -donors (N/O/F)
    weak complexation of -acceptors (olefins, phosphines)

    Typical catalysis: Polymerisation


    Me
    M

    Me
    M

    etc
    Me

    Transition-metal Organometallics

    "Middle" Transition Metals


    Groups 5-7

    Many accessible oxidation states


    Mostly 18e
    Ligands strongly bound
    Strong, not very reactive M-C bonds
    Preference for -donor/-acceptor combinations (CO!)
    Typical catalysis: Alkene and alkyne metathesis

    CH2

    CH2

    M CH2

    CH2
    M
    CH2
    CH2

    M CH2
    CH2

    CH2

    Transition-metal Organometallics

    Late Transition Metals


    Groups 8-10 (and 11)

    Many accessible oxidation states


    Mostly 18e or 16e
    16e common for square-planar complexes

    Easy ligand association/dissociation


    Weak, not very reactive M-C bonds
    Even weaker, reactive M-O/M-N bonds
    Preference for -donor/weak -acceptor ligands (phosphines)
    Typical catalysis: Hydroformylation
    H

    CO

    CO

    O
    H

    M
    H

    H2

    M
    H

    H2
    Transition-metal Organometallics

    Front- and Back-benchers

    1st row
    2nd row
    3rd row

    Transition-metal Organometallics

    Going down...
    1st row:
    often unpaired electrons
    different spin states (HS/LS) accessible
    "highest possible" oxidation states not very stable
    MnO4- is a strong oxidant

    2nd/3rd row:
    nearly always "closed shell"
    virtually same atomic radii (except Y/La)
    highest oxidation states fairly stable
    ReO4- is hardly oxidizing

    2nd row often more reactive than 3rd

    Transition-metal Organometallics

    M-H and M-C -bonds


    M H

    Hydride

    M C

    Alkyl

    M C

    Vinyl (alkenyl)

    M C C

    Acetylide (alkynyl)

    Aryl

    Transition-metal Organometallics

    Synthesis of metal alkyls

    Metathesis
    TiCl4 + 4 BzMgCl

    TiBz4 + 4 MgCl2
    (Bz = benzyl, C6H5CH2)

    Electrophilic attack on metal


    Mn(CO)5

    MeI

    Insertion

    MeMn(CO)5

    Ar

    Ar

    N
    N

    Co H
    N

    Co Et
    N

    Ar

    C2H4

    Ar
    Transition-metal Organometallics

    Synthesis of metal alkyls

    Oxidative addition
    often starts with electrophilic attack

    Me
    O

    O
    L MeI
    Rh
    O
    L

    O
    Rh

    L
    L

    L = P(OPh)3

    I
    L
    O
    I
    Rh
    O
    Me
    L

    L = PPh3

    10

    Transition-metal Organometallics

    Decomposition of metal alkyls


    Dominant: -hydrogen elimination
    M

    M
    H

    M
    H
    Alternatives:
    homolysis
    //-eliminations
    reductive elimination (especially with H or another alkyl)
    ligand metallation

    11

    Transition-metal Organometallics

    How to prevent -hydrogen elimination ?

    No -hydrogen
    CH3, CH2CMe3, CH2SiMe3, CH2Ph

    No empty site cis to alkyl


    Et

    Co

    N
    O

    N
    H

    O
    OH2

    Product of elimination unstable


    ?

    12

    Transition-metal Organometallics

    How to prevent -hydrogen elimination ?

    Planar transition state inaccessible


    H

    H
    L2Pt

    L2Pt H

    L2Pt

    ???

    even for 5-membered metallacycles -elimination is difficult !


    (basis of selective ethene trimerization)

    13

    Transition-metal Organometallics

    Reactions of metal alkyls

    Insertion, of both polar and non-polar C=X bonds:


    olefins, acetylenes, allenes, dienes
    (ketones etc)
    CO, isocyanides

    14

    Reductive elimination

    Transition-metal Organometallics

    Synthesis of metal hydrides

    Metathesis
    WCl6 + LiBEt3H + PR3

    -elimination

    WH6(PR3)3

    M
    H

    Protonation / oxidative addition


    H
    LnM

    HX

    LnM
    X
    +

    LnM H X-

    15

    LnM

    H2

    H
    LnM

    LnM H2
    H

    Transition-metal Organometallics

    Structure of WH6(PiPr2Ph)3

    16

    Transition-metal Organometallics

    Synthesis of metal hydrides

    Hydrogenolysis
    Ar

    Ar

    N
    N

    Co Et
    N

    17

    N
    H2

    Co H
    N

    Transition-metal Organometallics

    Reactivity of metal hydrides

    "Hydride is the smallest alkyl"

    Can react as H+ or H HCo(CO)4 nearly as acidic as H2SO4


    Cp2ScH gives H2 with acids, alcohols, ...

    Insertion reactions
    CO insertion rare (endothermic!)

    18

    Transition-metal Organometallics

    Metal aryls
    Usually much more stable than alkyls
    H
    H
    M
    M +

    ???

    Synthesis:
    Metathesis
    Oxidative addition
    Reaction/decomposition:
    Reductive elimination

    19

    Transition-metal Organometallics

    The other ligands...


    Common ligands for transition metals:
    ligands, CO, phosphines
    CO

    PR3

    General characteristic: -donating, -accepting, "soft"

    20

    Transition-metal Organometallics

    ligands, CO, phosphines


    -donor character:
    phosphines > alkenes, CO
    -acceptor character:
    CO > alkenes > phosphines
    Depends strongly on the substituents on P, C=C !

    21

    Transition-metal Organometallics

    Donor and acceptor orbitals


    -donor
    alkene

    -acceptor

    CO
    LP

    phosphine
    LP

    22

    Transition-metal Organometallics

    ligands, CO, phosphines

    CO is one of the best -acceptors (-acids)


    isocyanides are stronger donors, weaker acceptors

    PMe3 very weak -acceptor, good -donor


    PF3 nearly as strongly -acidic as CO

    C2H4 weak -acceptor


    C2(CN)4 very strong -acceptor
    even forms stable radical anions

    23

    Transition-metal Organometallics

    Synthesis of CO and -ligand complexes


    Stable, neutral ligands:
    generate empty site(s) in presence of free ligand
    reflux in
    Cr(CO)6
    Cr(CO)3(C6H6)
    C6H6
    1.13

    1.37

    1.417

    1.410

    2.223
    1.841

    1.913
    1.141

    24

    2.141

    1.157

    Transition-metal Organometallics

    Synthesis of CO and -ligand complexes


    Variation:
    reductive synthesis
    +
    CrCl3

    NiSO4

    25

    Al/AlCl3
    C6H6

    S2O42CO

    Cr

    + e-

    Cr

    Ni(CO)4

    Transition-metal Organometallics

    Synthesis of CO and -ligand complexes


    Anionic ligands:
    introduce via metathesis (Cp-), substitution
    or oxidative addition (allyl)

    FeCl2

    CpNa

    Fe

    Fe(CO)5

    Fe
    OC
    OC

    26

    CO

    Transition-metal Organometallics

    Synthesis of CO and -ligand complexes

    Cl

    Mn(CO)5
    or h

    27

    Mn(CO)5

    Mn(CO)4

    Transition-metal Organometallics

    Modification of ligands
    by H+/H- addition/abstraction
    +
    M

    H+
    - H+

    acid
    base

    M
    -

    28

    H- H-

    H- donor: NaBH4, LiBHEt3


    H- abstractor: Ph3C+ BF4-

    Transition-metal Organometallics

    Reactivity of -ligand complexes


    Ligand activated for nucleophilic attack
    both internal and external

    X-

    C O

    M C O

    M
    O

    29

    Transition-metal Organometallics

    Reactivity of -ligand complexes


    Change of hapticity

    30

    / allyl

    ring slippage

    Transition-metal Organometallics

    More than 18 e ?

    1.47
    1.40

    1.51
    2.33
    2.45

    1.95

    1.15

    1.22
    1.99

    2.97

    2.30-2.32

    2.46
    1.40

    2.35

    2.32

    1.41
    1.41-1.44
    1.40

    31

    Transition-metal Organometallics

    complexes
    A bond as 2-electron donor for a metal.
    H2 complexes (non-classical hydrides)
    CO H

    CO
    OC
    OC

    Cr

    CO
    CO

    h
    H2

    OC
    OC

    H
    CO

    CO

    CO

    Cr

    C-H bonds
    Usually intramolecular

    N
    Rh

    Pt
    L

    Sometimes intermolecular

    CO
    OC
    OC

    Cr

    CH4
    CO

    In "matrix"
    Characterized by IR

    CO

    32

    Transition-metal Organometallics

    complex ?

    2.10

    1.92

    N
    Rh
    H
    H

    33

    Transition-metal Organometallics

    complex ?

    +
    L

    L
    Pt
    H
    34

    Transition-metal Organometallics

    complexes

    C-Si bonds

    H
    Me3Si

    La

    THF
    H

    SiMe3

    Me3Si Me Si Me
    Me

    2.63
    3.22

    103

    35

    Transition-metal Organometallics

    complexes

    Si-H bonds

    OC
    OC

    36

    Mn

    SiHPh2

    ??

    etc: B-H, Sn-Cl, P-H, ..

    Transition-metal Organometallics

    complexes
    A complex is an (arrested) intermediate for oxidative addition:
    M

    XY

    X
    Y

    X
    M
    Y

    M(m)

    M(m)

    M(m+2)

    n-e

    (n+2)-e

    (n+2)-e

    Stable complexes are formed when the metal is not


    -basic enough to enable completion of the addition.

    37

    Transition-metal Organometallics

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