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Reactivity of Coordinated Nitriles − Formation of the Acetamidine Complex cis ‐[(PMe 3 ) 2 Pt{1‐MeTy(−H)}{CH 3 C(NH)NH 2 }] + from the 1‐Methylthyminate Compound cis ‐[(PMe 3 ) 2 Pt{1‐MeTy(−H)}(CH 3 CN)] + − Synthesis, Characterisation, and X‐ray Structures
Author(s) -
Longato Bruno,
Bandoli Giuliano,
Mucci Adele,
Schenetti Luisa
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200112)2001:12<3021::aid-ejic3021>3.0.co;2-f
Subject(s) - chemistry , acetonitrile , ligand (biochemistry) , perchlorate , medicinal chemistry , nitrile , denticity , reactivity (psychology) , aqueous solution , acetamide , pincer movement , yield (engineering) , stereochemistry , inorganic chemistry , crystal structure , crystallography , organic chemistry , catalysis , medicine , alternative medicine , pathology , ion , biochemistry , materials science , receptor , metallurgy
1‐Methylthymine (1‐MeTy) reacts reversibly with the hydroxo complexes cis ‐[(PMe 3 ) 2 Pt(μ‐OH)] 2 X 2 (X − = NO 3 ; ClO 4 ) in various solvents (S = CH 3 CN, H 2 O, DMSO) to give the thyminate derivatives cis ‐[(PMe 3 ) 2 Pt{1‐MeTy(−H)}(S)]X that have been isolated as pure compounds when S is CH 3 CN. The single‐crystal X‐ray structure of cis ‐[(PMe 3 ) 2 Pt{1‐MeTy(−H)}(CH 3 CN)]ClO 4 shows that the N(3)‐platinated nucleobase acts as a monodentate ligand and a molecule of CH 3 CN completes the coordination sphere of the metal. Crystals of the acetamidine derivative cis ‐[(PMe 3 ) 2 Pt{1‐MeTy(−H)}{CH 3 C(NH)NH 2 }]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 NH 3 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 NH 3 was added to cis ‐[(PMe 3 ) 2 Pt{1‐MeTy(−H)}(CH 3 CN)] + dissolved in CH 3 CN. Side products of this reaction are the ammonia complex cis ‐[(PMe 3 ) 2 Pt{1‐MeTy(−H)}(NH 3 )] + , 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.