Reactivity of coordinated nitriles - Formation of the acetamidine complex cis-[(PMe3)(2)Pt{1-MeTy(-H)}{CH3C(NH)NH2}](+) from the 1-methylthyminate compound cis-[(PMe3)(2)Pt{1-MeTy(-H)}(CH3CN)](+) - Synthesis, characterisation, and X-ray structures
B. Longato et al., Reactivity of coordinated nitriles - Formation of the acetamidine complex cis-[(PMe3)(2)Pt{1-MeTy(-H)}{CH3C(NH)NH2}](+) from the 1-methylthyminate compound cis-[(PMe3)(2)Pt{1-MeTy(-H)}(CH3CN)](+) - Synthesis, characterisation, and X-ray structures, EUR J INORG, (12), 2001, pp. 3021-3029
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 t
hat the N(3)-platinated nucleobase acts as a monodentate ligand and a molec
ule of CH3CN completes the coordination sphere of the metal. Crystals of th
e acetamidine derivative cis-[(PMe3)(2)Pt{1-MeTy(-H)}{CH3C(NH)NH2}]X were i
solated from an acetonitrile solution of this complex, in the presence of s
mall amounts of water, after several months at room temperature, separated
in 5-10% yield. The X-ray analysis of the perchlorate salt shows a configur
ation of the amidine ligand consistent with a formal trans addition of NH3
to the CN triple bond of the coordinated nitrile. The acetamidine complex w
as 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. S
ide products of this reaction are the ammonia complex cis-[(PMe3)(2)Pt{1-Me
Ty(-H)}(NH3)](+), which was also obtained as pure compound, acetamide, and
other platinum containing species. All the isolated complexes were characte
rised by elemental analysis, IR, and multinuclear NMR spectroscopy.