1-Methylthymine (1-MeTy) reacts reversibly with the hydroxo complexes cis-[(PMe3)(2)Pt(mu -OH)](2)X-2 (X- = NO3; ClO4) in various solvents (S = CH3CN, H2O, DMSO) to give the thyminate derivatives cis-[(PMe3)(2)Pt{1-MeTy(-H)}(S)]X that have been isolated as pure compounds when S is CH3CN. The single-crystal X-ray structure of cis-[(PMe3)(2)Pt{1-MeTy(-H)}(CH3CN)]ClO4 shows that the N(3)-platinated nucleobase acts as a monodentate ligand and a molecule of CH3CN completes the coordination sphere of the metal. Crystals of the acetamidine derivative cis-[(PMe3)(2)Pt{1-MeTy(-H)}{CH3C(NH)NH2}]X were isolated from an acetonitrile solution of this complex, in the presence of small amounts of water, after several months at room temperature, separated in 5-10% yield. The X-ray analysis of the perchlorate salt shows a configuration of the amidine ligand consistent with a formal trans addition of NH3 to the CN triple bond of the coordinated nitrile. The acetamidine complex was formed in high yield (70%), in a few weeks, when aqueous solution of NH3 was added to cis-[(PMe3)(2)Pt{1-MeTy(-H)}(CH3CN)](+) dissolved in CH3CN. Side products of this reaction are the ammonia complex cis-[(PMe3)(2)Pt{1-MeTy(-H)}(NH3)](+), which was also obtained as pure compound, acetamide, and other platinum containing species. All the isolated complexes were characterised by elemental analysis, IR, and multinuclear NMR spectroscopy.
Reactivity of coordinated nitriles - Formation of the acetamidine complex cis-[(PMe3)(2)Pt{1-MeTyH)}{CH3C(NH)NH2}](+) from the 1-methylthyminate compound cis-[(PMe3)(2)Pt{1-MeTyH)}(CH3CN)](+) - Synthesis, characterisation, and X-ray structures / B., Longato; G., Bandoli; Mucci, Adele; Schenetti, Luisa. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - STAMPA. - 2001:12(2001), pp. 3021-3029. [10.1002/1099-0682(200112)2001:12<3021::AID-EJIC3021>3.0.CO;2-F]
Reactivity of coordinated nitriles - Formation of the acetamidine complex cis-[(PMe3)(2)Pt{1-MeTyH)}{CH3C(NH)NH2}](+) from the 1-methylthyminate compound cis-[(PMe3)(2)Pt{1-MeTyH)}(CH3CN)](+) - Synthesis, characterisation, and X-ray structures
MUCCI, Adele;SCHENETTI, Luisa
2001
Abstract
1-Methylthymine (1-MeTy) reacts reversibly with the hydroxo complexes cis-[(PMe3)(2)Pt(mu -OH)](2)X-2 (X- = NO3; ClO4) in various solvents (S = CH3CN, H2O, DMSO) to give the thyminate derivatives cis-[(PMe3)(2)Pt{1-MeTy(-H)}(S)]X that have been isolated as pure compounds when S is CH3CN. The single-crystal X-ray structure of cis-[(PMe3)(2)Pt{1-MeTy(-H)}(CH3CN)]ClO4 shows that the N(3)-platinated nucleobase acts as a monodentate ligand and a molecule of CH3CN completes the coordination sphere of the metal. Crystals of the acetamidine derivative cis-[(PMe3)(2)Pt{1-MeTy(-H)}{CH3C(NH)NH2}]X were isolated from an acetonitrile solution of this complex, in the presence of small amounts of water, after several months at room temperature, separated in 5-10% yield. The X-ray analysis of the perchlorate salt shows a configuration of the amidine ligand consistent with a formal trans addition of NH3 to the CN triple bond of the coordinated nitrile. The acetamidine complex was formed in high yield (70%), in a few weeks, when aqueous solution of NH3 was added to cis-[(PMe3)(2)Pt{1-MeTy(-H)}(CH3CN)](+) dissolved in CH3CN. Side products of this reaction are the ammonia complex cis-[(PMe3)(2)Pt{1-MeTy(-H)}(NH3)](+), which was also obtained as pure compound, acetamide, and other platinum containing species. All the isolated complexes were characterised by elemental analysis, IR, and multinuclear NMR spectroscopy.File | Dimensione | Formato | |
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