ISSN:
1434-1948
Keywords:
Substitution mechanism
;
Platinum
;
Pressure dependence
;
Kinetics
;
Dinuclear complex
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Both reaction steps observed for the substitution of water by thiourea in the complexes [Pt(en)(OH2)2]2+ and [Pt(phen)(OH2)2]2+ (en = ethylenediamine, phen = 1,10-phenanthroline) were investigated under pseudo-first-order conditions using the stopped-flow technique. The substitution of the second water molecule in each complex was also studied under high pressure. The observed pseudo-first-order rate constants kobs (s-1) obeyed the equation k1,2obs= k1,2[tu] (tu = thiourea), where “1” and “2” refer to the first and the second substitution reactions, respectively. Kinetic parameters associated with the substitution process are: k1en (25.0°C, pH = 3.0, I = 0.1 M) = 25.6 M-1 s-1, ΔH# = 51 kJ mol-1, ΔS# = -48 J K-1 mol-1; k2en (same conditions) = 12.1 M-1 s-1, ΔH# = 30 kJ mol-1, ΔS# = -124 J K-1 mol-1, ΔV# = -7 cm3 mol-1; k1phen (25.0°C, pH = 1.0, I = 0.1 M) = 2900 M-1 s-1, ΔH# = 41 kJ mol-1, ΔS# = -41 J K-1 mol-1; k2phen (same conditions) = 1170 M-1 s-1, ΔH# = 37 kJ mol-1, ΔS#= -61 J K-1 mol-1, ΔV# = -5 cm3 mol-1. The temperature and pressure dependence of all the processes studied suggest an associative substitution mechanism. The hydroxo-bridged dinuclear complex [{Pt(phen)(μ-OH)}2]2+ is formed from [Pt(phen)(OH2)2]2+ in aqueous solution unless the solution is very dilute and highly acidic. The X-ray structure of [{Pt(phen)(μ-OH)}2](F3CSO3)2 · 2 H2O was determined. It belongs to the triclinic space group P1 and has one formula unit in the unit cell. The unit cell dimensions are a = 7.126(5), b = 9.665(5), c = 12.774(7) Å; α = 71.85(5), β = 85.52(5), γ = 73.12(5) deg; V = 799.9(8) Å3. The structure was solved with the Patterson method and refined to R = 0.061. A square planar coordination of the platinum centers is observed, with no deviations from planarity but distortions due to the small bite angle of phen and the four-membered ring. No significant lengthening of the Pt-O bond [mean value: 2.03(1) Å] is observed in comparison with [{Pt(NH3)2(μ-OH)}2]2+.
Type of Medium:
Electronic Resource
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