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    Hard and Soft Acid and Bases

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    Dr. Md. Ehtesham Ul Hoque
    1. The hard and soft acid and base (HSAB) theory categorizes acids and bases as either hard or soft based on their size, polarizability, and charge density. Hard acids prefer hard bases which are small, less polarizable, and have high charge density like oxygen, nitrogen, and fluorine. 2. Soft acids prefer soft bases which are larger, more polarizable, and have lower charge density like phosphorus, sulfur, and iodine. Combinations of hard-hard and soft-soft acid-base pairs are more stable due to better orbital matching. 3. The HSAB principle is useful for predicting reaction feasibility, complex stability, and ligand binding preferences in areas like

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    Hard and Soft Acid and Bases

    Uploaded by

    Dr. Md. Ehtesham Ul Hoque
    457 views15 pages
    1. The hard and soft acid and base (HSAB) theory categorizes acids and bases as either hard or soft based on their size, polarizability, and charge density. Hard acids prefer hard bases which are small, less polarizable, and have high charge density like oxygen, nitrogen, and fluorine. 2. Soft acids prefer soft bases which are larger, more polarizable, and have lower charge density like phosphorus, sulfur, and iodine. Combinations of hard-hard and soft-soft acid-base pairs are more stable due to better orbital matching. 3. The HSAB principle is useful for predicting reaction feasibility, complex stability, and ligand binding preferences in areas like

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    HSAB Theory

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    1. The hard and soft acid and base (HSAB) theory categorizes acids and bases as either hard or soft based on their size, polarizability, and charge density. Hard acids prefer hard bases which are small, less polarizable, and have high charge density like oxygen, nitrogen, and fluorine. 2. Soft acids prefer soft bases which are larger, more polarizable, and have lower charge density like phosphorus, sulfur, and iodine. Combinations of hard-hard and soft-soft acid-base pairs are more stable due to better orbital matching. 3. The HSAB principle is useful for predicting reaction feasibility, complex stability, and ligand binding preferences in areas like

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    457 views15 pages

    Hard and Soft Acid and Bases

    Uploaded by

    Dr. Md. Ehtesham Ul Hoque
    1. The hard and soft acid and base (HSAB) theory categorizes acids and bases as either hard or soft based on their size, polarizability, and charge density. Hard acids prefer hard bases which are small, less polarizable, and have high charge density like oxygen, nitrogen, and fluorine. 2. Soft acids prefer soft bases which are larger, more polarizable, and have lower charge density like phosphorus, sulfur, and iodine. Combinations of hard-hard and soft-soft acid-base pairs are more stable due to better orbital matching. 3. The HSAB principle is useful for predicting reaction feasibility, complex stability, and ligand binding preferences in areas like

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 15

    Hard and Soft Acid and Bases

    Lewis Acids & Bases


    A base is an electron-pair donor, and an acid is an electron-pair acceptor. The
    two combine to form an adduct.
    A + :B  A-B
    In complexes metals are electron acceptors hence they are acids and Ligands
    give lone pair of electrons and are bases. Metals were divided into two
    categories

    Class A/Type I Class B/Type II


    1.Alkali and alkaline earths Transition metals lower OS
    2. TM in higher OS Large size
    3. Small size Less electropositive
    4. Highly electropositive
    Hard and Soft Acids
    R.G. Pearson (1963) categorized acids and bases as either hard or soft (using Kf
    values).

    Hard acids
    1. Alkali and alkaline earths

    2. TM in higher OS

    3. Highly electropositive and very few electrons

    4. They are not very polarisable and prefer less polarisable ligands.

    5. Prefer complexes with ligands having donor atoms like N, O, F

    6. high charge density

    7. Their d orbitals are often unavailable to engage in π bonding.

    8. Hard Acids prefer to bond with Hard Bases


    Hard and Soft Acids
    Hard Bases
    1. Ligands having highly electronegative donor atoms – F, O, N
    2. They prefer complexes with hard acids.
    3. Less polarisable
    4. Small size
    5. Strength of hard bases –
    F>Cl> Br >O > S> Se>N> P>

    Soft Bases
    1. Donor atom is less electronegative – P,As,
    2. Large size
    3. High polarisability
    4. They prefer complexes with soft acids
    Acids
    Hard Acids Borderline Soft Acids
    H+, Li+, Na+, K+ BBr3,B(CH3)3 Cu+,Ag+, Au+,

    Be2+, Mg2+, Ca2+ Cd2+,Hg22+,

    BF3, BCl3, B(OR)3 BH3,Tl+, Tl(CH3)3 Hg2+, Pd2+,Pt2+,

    Al3+, AlCl3,AlH3 Pt4+


    Cr3+,Mn2+, Fe3+, Co3+ Fe2+,Co2+,Ni2+
    Cu2+,Zn2+,Rh3+
    Ir3+, Ru3+, Os2+
    Bases
    Hard Bases Borderline Soft Bases
    F-, Cl- Br- H-, I-
    H2O, OH-,O2- NO2-, N3- , N2 H2S, HS-, S2-
    ROH, RO-, R2O, CH3CO2- SO32- RSH, RS-, R2S
    NO3-, ClO4- SCN-, CN-, CO
    CO32-,SO42-, PO43- S2O32-
    NH3, RNH2 C6H5NH2 R3P, C6H6
    HSAB principle

    •Hard Acids prefer to bond with Hard Bases


    •Soft Acids prefer to bond with Soft Bases.
    •HA and HB are not polarisable so the bond is mostly ionic.
    •SA and SB is highly polarisable so the bond is covalent.
    Applications of Hard/Soft Theory
    1. Stability of a complex –
    A complex would be more stable if metal and ligand, both are hard or soft.

    eg – 1. AgI2- is stable but AgF2- is not.

    Ag+ + 2I-  AgI2-

    SA SB Stable complex

    Ag+ + 2F-  AgF2-

    SA HB Unstable

    2. [CoF6] 3- is more stable than [CoI6] 3-

    HA-HB HA-SB
    2. Feasibility of a reaction

    A reaction is favourable if the product follows HSAB rule, like combinations.


    Eg.
    LiI + CsF  LiF + CsI
    HA-SB SA-HB HA-HB SA-SB

    CaS + H 2O  CaO + H 2S
    HA-SB HB HA-HB SB

    3. The Qual Scheme, a series of chemical reactions used to separate


    and identify the presence of dozens of metal ions, is based largely on the
    hard and soft properties of the metal ions.
    The softer metals are precipitated out as chlorides or sulfides,
    with the harder ions formed as carbonates.
    4.Thiocyanate, an ambidentate ligand:

    SCN- vs. NCS- Thiocyanate (SCN-) is a particularly interesting ligand. It is


    ambidentate, and can bind to metal ions either through the S or the N.
    Obviously, it prefers to bind to soft metal ions through the S, and to hard
    metal ions through the N. This can be seen in the structures of [Au(SCN)2]-
    and [Fe(NCS)6]3- in the Figure below:
    Thiocyanate
    Complexes showing
    a) N-bonding in the
    [Fe(NCS)6]3-
    complex with the hard
    Fe(III) ion, and

    b) S-bonding in the
    [Au(SCN)2]- complex
    (CSD: AREKOX) with
    the soft Au(I) ion
    5. Evidence in Nature
    The chalcophile elements are typically found as sulfides or bonded
    to Se2- or Te2-. They include: Cd2+, Pb2+, Sb3+, and Bi3+. These are soft Lewis
    acids.
    6.
    Hard-soft considerations allow us to make reasonable predictions

    Hard acids tend to react better with hard bases and soft acids with soft
    bases, in order to produce hard-hard or soft-soft combinations

    In general, hard-hard combinations are energetically


    more favorable than soft-soft

    But there is more to it…

    An acid or a base may be hard or soft


    and at the same time it may be strong or weak

    Both characteristics must always be taken into account

    e.g. If two bases equally soft compete for the same acid,
    the one with greater basicity will be preferred
    but if they are not equally soft, the preference may be inverted

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