SlideShare utilise les cookies pour améliorer les fonctionnalités et les performances, et également pour vous montrer des publicités pertinentes. Si vous continuez à naviguer sur ce site, vous acceptez l’utilisation de cookies. Consultez nos Conditions d’utilisation et notre Politique de confidentialité.
SlideShare utilise les cookies pour améliorer les fonctionnalités et les performances, et également pour vous montrer des publicités pertinentes. Si vous continuez à naviguer sur ce site, vous acceptez l’utilisation de cookies. Consultez notre Politique de confidentialité et nos Conditions d’utilisation pour en savoir plus.
SWW – RN to BSN program –students needing core courses were taking them elsewhere – student retention, building SHU community UG core courses -History, English, Math launched in 2004 ID worked with faculty to develop courses 2005 – together with the TLTC, A&S, the EPC adopted QM as a best practice EPC added their recommendations to the essential elements How were we going to achieve this goal?
SO NJ - 20 min from NY Mobile Computing Program – every UG student gets a laptop or tablet pc – refreshed every 2 yrs Wireless campus Teaching, Learning and Technology Center 2 Sr. ID’s, 4 ID’s, 1 LMS coordinator, CTC, DMS team Each ID responsible for specific depts
Together with A&S, TLTC asked for volunteers to create online versions of their F2F course A Technology Teaching Assistant available to assist during the semester – must by a major in subject and have taken the course – in good standing and is tech savvy – work study
Why create a template – basic information is same – easier for faculty, consistent information EPC recommends 1 TD per week –atleast, Introduce yourself TD, Pirates Lounge, learning/tech contract Content guidelines – unit, structure, details, points, outcomes, calendar, netiquette, expectations… Sample course policies – grading rubric, clear late policy, College policies – academic integrity, contact numbers, where to get help University tech requirements – you must have… - may not be FT SHU students…
Updating technology New versions of Bb Lessons learned – are you ready to teach an online course, professional development, are you ready to take an online course Better ways of using technology
2. The classification of mechanisms
3. Ligand substitution in octahedral complexes
• The evidence for dissociative mechanisms
• Ligand substitution in Octahedral complexes without breaking metal-
4. Ligand substitution in square planar complexes
• Associative Mechanism at D4h Centers
• Factors Which Affect The Rate Of Substitution
5. Trans effect
6. Theories of trans effect
• Electrostatic Polarisation Theory
• Π Bonding Theory
• Molecular Orbital Theory for σ & π trans effects
7. Application of trans effect
One of the most general reactions exhibited by coordination
compounds is that of substitution, or replacement, of one ligand by
Ligand substitution involves the exchange of one ligand for
another, with no change in oxidation state at the metal center
[MLxX] + Y = [MLxY] + X
X is the leaving group and Y is the entering group.
Metal complexes that undergo substitution reactions with t1/2= 1
min. at 25 C are called kinetically labile. If t1/2 > 1 min., the
complex is kinetically inert (H. Taube).
Cr(III) complexes are generally inert.
Cu(II) complexes are generally very labile.
The classification of mechanisms
•The mechanism of a ligand substitution reaction is the sequence of
elementary steps by which the reaction takes.
• Types of Substitution Mechanisms:
1. Dissociative Reaction Mechanism
MLxX = MLx + X
MLx + Y = MLxY
formation of an intermediate
coordination number of the intermediate is lower than that in the starting
corresponds to SN1 mechanism for organic compounds
The classification of mechanisms
2. Associative Reaction Mechanism
MLxX + Y = MLxXY
MLxXY = MLxY + X
formation of an intermediate
coordination number of the intermediate is higher than that in the
3. Interchange Reaction Mechanism
MLxX + Y = Y--MLx--X = MLxY + X
Bond formation between the metal and entering group is
concurrent with bond cleavage between the metal and the leaving
corresponds to SN2 reaction in organic chemistry
Ligand substitution in
ML6 + Y = ML5Y + L
• For substitution reactions of octahedral metal
complexes the following is very often observed:
At high concentration of Y, the rate is
independent of [Y], suggesting a dissociative
mechanism. At low concentrations of Y, the rate
depends on [Y] and [ML6], suggesting an
The evidence for dissociative
a) The rate of reaction changes only slightly with changes in the
incoming ligand. If dissociation is r.d.s., the entering group should
have no effect at all on the reaction rate.
b) Decreasing negative charge or increasing positive charge on the
reactant complex decreases the rate of substitution. Larger
electrostatic attraction between the positive metal ion & the
negative ligand should slow the dissociation.
c) Steric crowding on the reactant complex increases the rate of
ligand dissociation. When ligands on the reactant are crowded, loss
of one of the ligands is made easier.
d) Activation energies & entropies are consistent with dissociation.
Ligand substitution in Octahedral complexes
without breaking metal-ligand bond
• In these substitution reactions, ligand exchange takes
place without the cleavage of metal-ligand bond.
• The metal-ligand bond is preserved.
• Example – The rapid conversion of carbonate ammine
cobalt(III) complexes into the corresponding aquo
complexes by the addition of excess acid.
• When the reaction is performed with O labelled water,
it is found that it is the O-O bond that breaks, rather
than Co-O bond.
• The observation that reactions involving fission of Co-
O bonds are invariably slow, confirms this result.
• Kinetic studies show the reacting species is the bicarbonato
complex [Co(NH ) CO H].
• It is formed by the attack of proton on oxygen atom
bonded to Co.
• Decarboxylation of this bicarbonate complex then occurs
as the rate determining step.
• This step is then followed by protonation to give the aquo
Ligand substitution in square planar
• ML3X + Y ML3Y + X
Initial attack by the entering group at a square planar Pt(II) centre is from
above or below the plane. Nucleophile Y then coordinates to give a
trigonal bipyramidal intermediate species which loses X with retention of
Associative Mechanism at D4h Centers
ML3X + Y ML3Y + X
+ NH3 [PtCl3(NH3)]-
The incoming ligand (colored blue)
approaches a vacant axial site of the square
planar complex to form a square pyramidal
intermediate (or transition state).
Intramolecular rearrangement via a trigonal
bipyramid generates a different square
pyramidal structure with the incoming
ligand now in the basal plane. (This motion
is closely related to Berry Pseudorotation).
The reaction is completed by the leaving
group departing from an axial site with
the stereochemistry being retained
during the substitution process.
Factors Which Affect The Rate Of
1) Role of the entering group
2) Role of the leaving group
3) Effect of the Metal Center
4) The trans effect
Role of the Entering Group:
• The rate of substitution is proportional to the nucleophilicity of
i.e. for most reactions of Pt(II), the rate constant increases in the order
: H2O <NH3 = py < Br-
• The ordering is consistent with Pt(II) being a soft metal center.
+ py [Pt(dien)(py)]+
• In H2O at 25o
C the sequence of lability is : H2O > Cl-
a spread of over 106
in rate across series.
The Role Of The Leaving Group:
Effect of the Metal Center
• The order of reactivity of a series of isovalent ions is: Ni(II) >
Pd(II) >> Pt(II)
• This order of reactivity is the same order as the tendency to form 5-
• More readily is the formation of a 5-coordinate intermediate
complex, the greater is the stabilization of the transition state and
so the greater is the bimolecular rate enhancement.
Ni k = 33 M-1
Pd k = 0.58 M-1
Pt k = 6.7 x 10-6
• The trans effect is best defined as the effect of a coordinated
ligand upon the rate of substitution of ligands opposite to it.
• Or The ability of a ligand in a square planar complex to direct the
replacement if the ligand trans to it.
• It was recognized by Werner (1893) and elaborated by Chernuyaev
• By comparing a large number of reaction rates Langford and Grey
set up a trans directing series.
• In the trans-directing series, the ligands are arranged in the
increasing order of trans effect as follows:
H2O < OH- < F- ≈ RNH2 ≈ py ≈ NH3< Cl- < Br-< SCN- ≈ I-
≈ NO2- ≈ C6H5- < SC(NH2)2≈ CH3-< NO ≈ H- ≈ PR3 <
C2H4 ≈ CN- ≈ CO
Theories of trans effect
• In order to explain the trans effect, several theories
have been proposed. Some of them are as listed :
1. Electrostatic Polarisation Theory
2. Π Bonding Theory
3. Molecular Orbital Theory for σ & π trans effects
1. Electrostatic Polarisation Theory
• This theory is primarily concerned with effect in the ground state.
• It was given by A.A. Grinberg.
• According to polarization theory, the ligand, by electrostatic effects,
weakens the bond trans to it and facilitates substitution in that
• Support for this theory is demonstrated by looking at the trans
> I- = SCN-
> py > NH3 > H2O
• The more polarizable ligands such as SCN-, and I- and the
ligands containing π-clouds e.g. CN- are high in the series..
• Less polarizable ligands such as ammonia or water are lower in
• Additional support comes from the observation that Pt(II)
complexes demonstrate a more pronounced trans effect than those
of the less polarizable Pd(II) and Ni(II) cations.
Electrostatic Polarisation Theory
• It explains the kinetic trans effect in square planar Pt(II)
2. Π Bonding Theory
• In the trigonal plane of the 5-coordinate transition state or intermediate, a
π-bonding interaction can occur between a metal d-orbital (e.g. dxy) and
suitable orbitals (p atomic orbitals, or molecular orbitals of π-symmetry) of
ligand L2(the ligand trans to the leaving group) and Y (the entering group).
• These 3 ligands and the metal center can communicate electronically
through π-bonding only if they all lie in the same plane in the transition
state or intermediate.
• In other words, strong trans directing ligands are those capable of forming
strong back bonding (π-acceptors), for example, CO, CN-, olefins etc. or
strong σ-donors such as CH3-, H-, PR3 etc. Strong π-donors such as H2O,
OH-, NH2-, etc. are weak in their trans directing properties.
3. Molecular Orbital Theory for σ & π
• The dx2-y2 orbital of Pt is involved in σ bonding in the square-planar
geometry, & both the dxz & dyz orbitals can contribute to π bonding in the
TBP transition state (5-coordinate species ).
• Any feature that stabilizes the TBP lowers the activation energy barrier &
speeds the reaction.
• TBP intermediate is stabilized by π-bonding.
•σ-bonding effects (ground-state effects) : The Pt-X bond is influenced by
the Pt-T bond, because both use the same Pt px & d2-y2 orbitals. When the
Pt-T σ bond is strong, it uses a larger part of these orbitals & leave less for the
Pt-X bond (weaker & higher in energy at its ground state; lower Ea).
Application of trans effect
1. Synthesis of isomers of Pt(NH3)2Cl2
2. Preparation of cis and trans PtCl2I(py) from PtCl4
1. Inorganic Chemistry (4th ed.). Shriver, D. F.; Atkins, P. W.
(2001). Oxford University Press
2. Inorganic Chemistry (3rd ed.). Miessler, G. L.; Tarr, D. A.
(2003). Pearson Prentice Hall
3. Chemical Principles (5th ed.). Zumdahl, Steven S (2005).
Houghton Mifflin Company
4. Inorganic Chemistry: Principles of Structure and Reactivity,
James E.Huheey, Ellen A.Keiter, Richard L.Keiter, Okhil
K.Medhi, Pearson Education, Delhi, 2006
5. Mechanisms of Inorganic Reactions : F. Basolo and R.
Pearson,, London, 1958.
6. Inorganic Chemistry ,By William W. Porterfield
7. Advances in Inorganic Chemistry, Volume 34, By A. G. Sykes