Substitution Reactions
2.4. Factors Influencing the Rate of Substitution Reactions
2.4.2. The Effect of the Entering Nucleophile
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A number of studies have been done to study the σ-and the π-trans effects of several ligands.
Some of the qualitative results reported are given in Table 2.1.[12] Good trans directing ligands are either strong or moderate σ and π bonding ligands.[12]
Table 2.1 Estimated relative σ- and π- trans effects of some ligands.[12]
* vs, very strong ; s, strong; m, medium; w, weak; vw, very weak
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1963.[45, 46] Hard acids (metal ions) are small and highly charged (eg: Li+ and Mg2+) and posses a valence electron shell which is not easily distorted while soft acids (metal ions) are large and posses low charge and have a valence electron shell which is easy to distort or remove.[8] Polarisability refers to the “softness” of the nucleophile. “Hard” nucleophiles prefers “hard” metal centres and
“soft” nucleophiles prefers “soft” substrates or metal centres.[8, 9, 47]
Platinum(II) being a soft metal centre prefers to be with soft donors. Thus, platinum(II) is more effective towards large donors.
c. Oxidability: Ligands that are readily oxidised are considered as good nucleophiles. The oxidability of the ligands can be characterised by their electrode reduction potential.
d. Solvation Energy: Easily solvated ligands are considered as weak nucleophiles. The ligand has to desolvate before it gets coordinated with the metal centre.
e. Metal Centre: Nucleophilicity depends much on the nature of the metal centre.
Heavier elements are better polarised in the transition state.
Earlier work had established the nucleophilic reactivity for platinum(II) with different nucleophiles.[15, 44] The most detailed study on the relative reactivity and nucleophilicity was done by Bellucco[25] for trans-Ptpy2Cl2 in methanol at 30 oC (Equation 2.20).[2]
Pt Cl Cl
py
py + Yn Pt + Cl-
Y Cl
py py
(n+1)
(2.20)
Trans-Pt(py)2Cl2 was used as the standard and the nucleophilic reactivity constants, nPt was defined as follows:[12][10]
npt
k k
S
log Y (2.21)
where kY = the rate constant for the reaction of the entering nucleophile kS = the rate constant for attack of the solvent (methanol).
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Some of the experimental results obtained are presented in Table 2.2.
Table 2. 2 Some nucleophilic constants given for Pt(py)2Cl2 with different nucleophiles of donor atoms.[12, 25, 48]
Nucleophile nPt Donor atom Nucleophile nPt Donor atom
CH3O- <2.4 O I 5.42 I (Halogen)
C6H5NH2 3.02 N Br 4.18 Cl (Halogen)
NH3 3.06 N 36Cl 3.04 Br (Halogen)
C5H5N 3.13 N (C6H5)P 8.79 P
H2N- NH2 3.85 N (C2H5)3P 8.85 P
(C6H5)2S 4.38 S (C6H5CH2)2Se 5.39 Se
S=C(NH2)2 7.17 S (CH3)2Se 5.56 Se
(CH3)2S 4.73 S (C6H5)3As 6.75 As
SCN 6.65 S (C2H5)3As 7.54 As
The nucleophilicity constant refers to the reactivity of the nucleophile towards platinum(II) and correlates with the other properties of the ligand.[12] This type of correlation is the linear free energy relationship (LFER). Brønsted[49] successfully applied the LFER to displacement reactions at hydrogen in various compound and a linear correlation between the log of the rate constant for the proton transfer and the log of the base strength of the reagent was found.[12]
For the platinum(II) complexes, plots of log kY verses nPt were observed to be linear (Figure 2.12). The linear free energy relationship is given by:[10, 12]
log kY = snPt + log kS (2.22) where the slope, s is complex specific and is called the nucleophilic discrimination factor. It is a measure of the sensitivity of the metal centre to the nucleophilicity of the incoming ligand.[12] If the value of s is large then that means the reaction is more sensitive to the
changes in the nucleophlic character. For trans-Pt(py)2Cl2, s is assigned to be 1. The y-intercept, log kS is the intrinsic reactivity of the complex. This gives the rate constant for
the weakest nucleophile measured in a solvent.[12] A smaller value of kS indicates that the complex is more sensitive to the changes in the nucleophile. Ligands that are capable of forming dative π-bonding with the platinum(II) in the transition state have larger values of s (smaller kS).[12] This enables the addition of the electrons from the nucleophile to the
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platinum(II) centre thereby making it easier for the entering group to take part in the transition state. The rate of reactions of such systems will exhibit a greater sensitivity towards the nucleophile.[12]
Generally larger s values are found for complexes of platinum(II) with softer base ligands.
However, few nucleophiles such asNO2 , SC(NH2) and SeCN do not obey the simple linear relationship between the log kS against nPt (Equation 2.22, Figure 2.12). The reason for this is due to the π-accepting abilities of the ligands which would lower the energy of the transition state.[2] This also depends up on the π-donor ability of the metal complex which makes some reagents more reactive towards some better π-donor metal complexes such as
2 4]
[PtCl or less reactive to certain complexes such as [Pt(dien)Br] than the reference complex, trans-Pt(py)2Cl2.[12]
Figure 2.12 Correlation of the rates of reaction of platinum(II) complexes with the standard trans- Pt(py)2Cl2 for different nucleophiles: •, trans-Pt(PEt3)2Cl2 in methanol at 30 oC; ▲, Pt(en)Cl2 in water at 35 oC.[12, 25, 32]
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Furthermore, recent studies have shown that nPtscale is best applied to neutral nucleophiles and the charge plays a greater role in determining the reactivity[37] while the effect of steric hindrance was found to play a minor role. [50]
2.4.3. The cis-Effect
The reactivity of platinum(II) complexes are less sensitive to the electronic displacement properties of cis ligands than trans ligands. However, they are more sensitive to the steric hindrance in the cis-position.[2] The trans effect is stronger by order of about 106 compared with the cis-effect.[8] Since the effect of cis-ligand is smaller, it is more difficult to study the cis effect by varying the cis ligands.
Research has shown that good trans activating ligands have poor cis-directing effects.[51, 52]
The experimental results obtained for cis-Pt(PEt3)2LCl with pyridine (Equation 2.23) have shown the same trend for the corresponding trans-Pt(PEt3)2LCl with pyridine with the change of the trans ligand, L in the order of CH3 > C6H5 > Cl .[53] The order of the reaction with the cis complex increased by a factor of three (Table 2.3)[10] while the order was much higher for the trans complex.[12]
cis-Pt(PEt3)2LCl + py cis-Pt(PEt3)2L(py) + Cl (2.23)
Table 2.3 The effect of trans ligand, L on the rate of reaction of cis-Pt(PEt3)2LCl with py.[53]
L k1(102 s-1)
Cl 1.7
6 6H
C 3.8
CH3 6
For a square planar complex which undergoes an associative mechanism, an, increase in the size of the incoming ligand would decrease the rate of substitution reaction. The orientation of the aromatic ring is perpendicular to the plane of the molecule and the nucleophile attacks either from above or below (Figure 2.3) of the plane and thus blocks the metal centre. This is further discussed in Section 2.4.4.
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Experimental results have shown that for some platinum(II) complexes with weakly trans directing ligands, the cis neighbour has shown a greater influence on the kinetics than the trans neighbour.[2]