The cationic platinum(II) complex [Pt(terpy)Cl]+ (terpy = 2,2'-6',2"-terpyridine), monomer in water at low concns. (<1.5 × 10-5 mol dm-3), undergoes basic and acid hydrolysis. The equil. const. for the acid hydrolysis is 1.4 × 10-5 mol dm-3 {25°C, [CH3SO3H] = 0.1 mol dm-3}. Basic hydrolysis (pH > 10) leads to the complete formation of [Pt(terpy)(OH)]+ with a two terms rate law, kobs = k1 + k2[OH-] (k1 = 2.24 × 10-2s-1, k2 = 0.7 mol-1 dm3 s-1). The mechanism of substitution is discussed and the system is compared to that of the congener [Pt(dien)Cl]+ species (dien = 1,5-diamino-3-aza-pentane). The crystal structure of [Pt(terpy)OH]ClO4·H2O has been detd.: monoclinic, space group P21/n, a 7.937(1), b 17.251(1), c 12.245(1) Å; β 95.50(1)°. The Pt-O distance is 1.999(5) Å, and the hydroxo group forms strong hydrogen bonds with the mol. of water of crystn. At. coordinates are given.
Kinetics and Equilibria in the Hydrolysis of [Pt(terpy)Cl]Cl; Crystal and Molecular Structure of [Pt(terpy)OH]ClO4.H2O (terpy=2,2 '-6,2 ''-terpyridine) / G., Annibale; L., Cattalini; Cornia, Andrea; FABRETTI COSTANTINO, Antonio; F., Guidi. - In: INORGANIC REACTION MECHANISMS. - ISSN 1028-6624. - STAMPA. - 2:3(2000), pp. 185-193.
Kinetics and Equilibria in the Hydrolysis of [Pt(terpy)Cl]Cl; Crystal and Molecular Structure of [Pt(terpy)OH]ClO4.H2O (terpy=2,2 '-6,2 ''-terpyridine)
CORNIA, Andrea;FABRETTI COSTANTINO, Antonio;
2000
Abstract
The cationic platinum(II) complex [Pt(terpy)Cl]+ (terpy = 2,2'-6',2"-terpyridine), monomer in water at low concns. (<1.5 × 10-5 mol dm-3), undergoes basic and acid hydrolysis. The equil. const. for the acid hydrolysis is 1.4 × 10-5 mol dm-3 {25°C, [CH3SO3H] = 0.1 mol dm-3}. Basic hydrolysis (pH > 10) leads to the complete formation of [Pt(terpy)(OH)]+ with a two terms rate law, kobs = k1 + k2[OH-] (k1 = 2.24 × 10-2s-1, k2 = 0.7 mol-1 dm3 s-1). The mechanism of substitution is discussed and the system is compared to that of the congener [Pt(dien)Cl]+ species (dien = 1,5-diamino-3-aza-pentane). The crystal structure of [Pt(terpy)OH]ClO4·H2O has been detd.: monoclinic, space group P21/n, a 7.937(1), b 17.251(1), c 12.245(1) Å; β 95.50(1)°. The Pt-O distance is 1.999(5) Å, and the hydroxo group forms strong hydrogen bonds with the mol. of water of crystn. At. coordinates are given.
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