Irreversible Insertion of Benzonitrile into Platinum(II)-Nitrogen Bonds of Nucleobase Complexes. Synthesis and Structural Characterisation of Stable Azametallacycle Compounds

Deprotonation of 1-methylcytosine( 1-MeCy ) and 9-methyladenine (9-MeAd) promoted by cis-[L2Pt(?-OH)]2(NO3)2 (L=PPh3, PMePh2, 1/2 dppe) in PhCN causes the irreversible insertion of a nitrile molecule into the Pt -N4 and Pt-N6 bonds of the cytosinate and adeninate ligands, respectively, to form the stable azametallacycle complexes cis-[L2PtNH=C(Ph){1-MeCy(-2H)}]NO3 (L=PPh3, 1; PMePh2, 2; 1/2 dppe,3) and cis-[L2PtNH=C(Ph){9-MeAd(-2H)}]NO3 (L=PPh3, 4; PMePh2, 5) containing the deprotonated form of the molecules (Z)-9-N-(1-methyl-2-oxo-2,3-dihydropyrimidin-4(1H)-ylidene)benzimidamide and (Z)-N-(9-methyl-1 H-purin-6(9H)-ylidene)benzimidamide. Single-crystal X-ray ana-lyses of 2 and 4 show the metal coordinated to the N3 cytosine site [Pt-N3 = 2.112(7) A?] and to the N1 site of adenine [Pt-N1 = 2.116(6) A?] and to the nitrogen atom of the inserted benzonitrile [Pt-N2 = 2.043(6) and 2.010 (6) A? in 2 and 4, respectively] , with the exocyclic nucleobase amino nitrogen bound to the carbon atom of the CN group. Complex 2, in solution, undergoes a dynamic process related to a partially restricted rotation around Pt-P bonds, arising from a steric interaction of the oxygen atom of the cytosine with one ring of the phosphine ligands. The reaction of 4 with acetylacetone (Hacac) causes the quantitative protonation of the anionic ligand, affording the acetylacetonate complex cis-[( PPh3)2Pt-(acac )]NO3 and the free benzimidamide NH=C(Ph){9-MeAd(-H)}. In the same experimental conditions, complex 3 reacts with Hacac only partially.