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    Thermodynamic and Kinetic Aspects of Metal Complexes

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    Wiratama Nugroho
    Stable complexes have a large positive ΔG° for ligand substitution reactions, making them inert. Inert complexes also have a large positive ΔG‡ for activation. Kinetic lability increases with increasing charge to radius ratio and decreasing crystal field stabilization energy. Ligand exchange can occur through dissociative, associative, or interchange mechanisms. The trans effect influences substitution kinetics in square planar complexes. Electron transfer between metal complexes can occur through outer sphere or inner sphere mechanisms, with the latter being much faster.

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    Thermodynamic and Kinetic Aspects of Metal Complexes

    Uploaded by

    Wiratama Nugroho
    242 views27 pages
    Stable complexes have a large positive ΔG° for ligand substitution reactions, making them inert. Inert complexes also have a large positive ΔG‡ for activation. Kinetic lability increases with increasing charge to radius ratio and decreasing crystal field stabilization energy. Ligand exchange can occur through dissociative, associative, or interchange mechanisms. The trans effect influences substitution kinetics in square planar complexes. Electron transfer between metal complexes can occur through outer sphere or inner sphere mechanisms, with the latter being much faster.

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    Senyawa kompleks

    Original Title

    Ch3

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    Stable complexes have a large positive ΔG° for ligand substitution reactions, making them inert. Inert complexes also have a large positive ΔG‡ for activation. Kinetic lability increases with increasing charge to radius ratio and decreasing crystal field stabilization energy. Ligand exchange can occur through dissociative, associative, or interchange mechanisms. The trans effect influences substitution kinetics in square planar complexes. Electron transfer between metal complexes can occur through outer sphere or inner sphere mechanisms, with the latter being much faster.

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    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    242 views27 pages

    Thermodynamic and Kinetic Aspects of Metal Complexes

    Uploaded by

    Wiratama Nugroho
    Stable complexes have a large positive ΔG° for ligand substitution reactions, making them inert. Inert complexes also have a large positive ΔG‡ for activation. Kinetic lability increases with increasing charge to radius ratio and decreasing crystal field stabilization energy. Ligand exchange can occur through dissociative, associative, or interchange mechanisms. The trans effect influences substitution kinetics in square planar complexes. Electron transfer between metal complexes can occur through outer sphere or inner sphere mechanisms, with the latter being much faster.

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    of 27

    Chapter 3

    Thermodynamic and kinetic


    aspects of metal complexes
    Conclusions from these examples.
    Stable complexes have a large POSITIVE GoRXN for ligand substitution and
    Inert complexes have a large POSITIVE G‡ (activation).

    Stability and Coordination Complexes ([MLn]x+)


    Typically expressed in terms of an overall formation or stability constant.
    (This is Kst on the Chemistry Data sheet you receive with exams)

    [MLn ]x 
    [M]x+ + nL [MLn]x+ K st  x
    [M(aq) ][L]n
    BUT, this does not occur in one fell swoop!!
    Water molecules do not just all fly off and are immediately replaced by nL ligands.

    [M] x+(aq) + L  [ML]x+ K1

    [ML(n-1)]x+ + L [MLn]x+ Kn

    Ks are the stepwise formation constants and provide insight into


    the solution species present as a function of [L].
    Stepwise formation constants
    These formation constants provide valuable information given that different species may
    have VERY DIFFERENT properties…including environmental impact. Such information
    provides selective isolation of metal ions from solution through reaction with ligands.

    For formation of divalent alkaline earth


    and 3d M2+ TM ions the Irving-
    Williams Series holds true.

    Ba<Sr<Ca<Mg<Mn<Fe<Co<Ni<Cu>Zn

    What is contributing to this trend?

    1. Charge to radius ratio.


    2. CFSE (beyond Mn2+)
    Jahn-Teller Distortion
    3. Hard-Soft Acids/Bases

    See R-C p 450-451.


    Associative Mechanism
    ML5X + Y ML5Y + X

    Step 1. Collision of ML5X with Y to yield a 7-coordinate intermediate. (slow)


    K1
    ML5X + Y ML5XY (slow, rate determining)

    X Y
    L L
    L L
    M
    L
    L M
    L X
    L Y
    L L
    Capped Pentagonal
    Octahedron Bipyramid
    Step 2. Cleavage of the M-X bond. (fast)

    ML5XY ML5Y + X (fast)

    The rate law for this process is rate = K1[ML5X][Y] (the units of K1 are sec-1Mole-1)
    If we find a reaction follows this rate law we conclude it is associative.
    Substitution reactions

    MLn + L' MLn-1L' + L

    Labile complexes <==> Fast substitution reactions (< few min)


    Inert complexes <==> Slow substitution reactions (>h)
    a kinetic concept

    Not to be confused with


    stable and unstable (a thermodynamic concept Gf <0)

    Inert Intermediate Labile


    d3, low spin d4-d6& d8 d8 (high spin) d1, d2, low spin d4-d6& d7-d10
    Mechanisms of ligand exchange reactions
    in octahedral complexes

    MLnX + Y MLnY + X

    Dissociative (D) Associative (A)


    MLn X MLn Y MLn X MLn Y

    X MLn Y Y MLn XY X

    Interchange (I)
    MLn X MLn Y

    Y X
    [ML n]°

    Ia if association X Y Id if dissociation
    is more important is more important
    Kinetics
    of dissociative reactions
    Fast equilibrium
    Kinetics K1 = k1/k-1
    of interchange reactions
    k2 << k-1

    For [Y] >> [ML5X]


    Kinetics of associative reactions
    Principal mechanisms of ligand exchange in octahedral complexes

    Dissociative

    Associative
    Dissociative pathway
    (5-coordinated intermediate)

    MOST COMMON

    Associative pathway
    (7-coordinated intermediate)
    Experimental evidence for dissociative mechanisms

    Rate is independent of the nature of L


    Experimental evidence for dissociative mechanisms

    Rate is dependent on the nature of L


    Labile or inert?
    L
    L L
    M
    L L

    Ea L
    L L
    L M
    L L L L
    M X
    L L
    X G

    LFAE = LFSE(sq pyr) - LFSE(oct)


    Why are some configurations inert and some are labile?

    Inert !
    Substitution reactions in square-planar complexes
    the trans effect

    L X L Y
    +X, -Y
    M M
    T L T L

    (the ability of T to labilize X)


    Trans Effect Strengths

    I. Trans effect is more pronounced for s donor


    as follows:
    OH-<NH3<Cl-<Br-<CN-,CO, CH3-<I-<PR3
    • Trans effect is more pronounced for a ð
    acceptor as follows:
    Br-<Cl-<NCS-<NO2-<CN-<CO
    Synthetic applications
    of the trans effect
    B. Substitution in trans complexes
    1) 3 possible substitution reactions for trans-[M(LL)2BX] + Y

    a) Retention of configuration with


    a square pyramidal intermediate

    b) Trigonal bipyramidal intermediate


    with B in the plane gives a mixture
    of products

    c) Trigonal bipyramidal intermediate


    with B axial leads to cis product
    2) Experimental Data
    a) Many factors determine the mixture of isomers in the product
    b) Example: Identity of X

    c) Prediction is very difficult without experimental data on related complexes

    C. Substitution in cis complexes

    1) The same 3 possibilities exist as for trans

    1) The products are just as hard to predict


    D. Isomerization of Chelate Complexes
    1) One mechanism is simple dissociation and reattachment of one donor of the
    ligand. This would be identical to any other substitution reaction

    2) Pseudorotation
    a) “Bailar Twist” = Trigonal twist = all three rings move together through a
    parallel intermediate
    b) Tetragonal Twists = one ring stays the same and the others move

    Bailar Twist Tetragonal Twist

    Tetragonal Twist Bailar Twist


    Electron transfer (redox) reactions

    -1e (oxidation)

    M1(x+)Ln + M2(y+)L’n M1(x +1)+Ln + M2(y-1)+L’n

    +1e (reduction)

    Very fast reactions (much faster than ligand exchange)

    May involve ligand exchange or not

    Very important in biological processes (metalloenzymes)


    Outer sphere mechanism

    [Fe(CN)6]4- + [IrCl6]2- [Fe(CN)6]3- + [IrCl6]3-

    [Co(NH3)5Cl]2+ + [Ru(NH3)6]2+ [Co(NH3)5Cl]+ + [Ru(NH3)6]3+

    Reactions ca. 100 times faster


    than ligand exchange A B "solvent cage"
    (coordination spheres remain the same)

    r = k [A][B]

    Ea
    Tunneling A + B A' + B'
    mechanism

    G
    Inner sphere mechanism

    [Co(NH3)5Cl)]2+ + [Çr(H2O)6]2+ [Co(NH3)5Cl)]2+:::[Çr(H2O)6]2+

    [Co(NH3)5Cl)]2+:::[Çr(H2O)6]2+ [CoIII(NH3)5(m-Cl)ÇrII(H2O)6]4+

    [CoIII(NH3)5(m-Cl)ÇrII(H2O)6]4+ [CoII(NH3)5(m-Cl)ÇrIII(H2O)6]4+

    [CoII(NH3)5(m-Cl)ÇrIII(H2O)6]4+ [CoII(NH3)5(H2O)]2+ + [ÇrIII(H2O)5Cl]2+

    [CoII(NH3)5(H2O)]2+ [Ço(H2O)6]2+ + 5NH4+


    Inner sphere mechanism

    k1 k3
    Ox-X + Red Ox-X-Red Ox(H2O)- + Red-X+
    k2 k4

    Reactions much faster


    than outer sphere electron transfer
    Ox-X-Red
    (bridging ligand often exchanged)

    r = k’ [Ox-X][Red] k’ = (k1k3/k2 + k3) Tunneling


    through bridge
    mechanism
    Ea
    Ox-X + Red
    Ox(H2O) - + Red-X +

    G

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