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


    Montagner, Diego and Venzo, Alfonso and Zangrando, Ennio and Longato, Bruno (2010) Irreversible Insertion of Benzonitrile into Platinum ( II ) - Nitrogen Bonds of Nucleobase Complexes. Synthesis and Structural Characterization of Stable Azametallacycle Compounds. Inorganic Chemistry, 49. pp. 2103-2110. ISSN 0020-1669

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    Abstract

    Deprotonation of 1-methylcytosine (1-MeCy) and 9-methyladenine (9-MeAd) promoted by cis-[L2Pt(μ-OH)]2(NO3)2 (L = PPh3, PMePh2, 1/2dppe) 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; 1/2dppe, 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-1H-purin-6(9H)-ylidene)benzimidamide. Single-crystal X-ray analyses of 2 and 4 show the metal coordinated to the N3 cytosine site [Pt−N3 = 2.112(7) Å̊] and to the N1 site of adenine [Pt−N1 = 2.116(6) Å̊] and to the nitrogen atom of the inserted benzonitrile [Pt−N2 = 2.043(6) and 2.010(6) Å̊ 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.

    Item Type: Article
    Keywords: Irreversible Insertion; Benzonitrile; Platinum(II)−Nitrogen Bonds; Nucleobase Complexes; Synthesis; Structural Characterization; Stable Azametallacycle Compounds;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 7061
    Identification Number: https://doi.org/10.1021/ic901508w
    Depositing User: Diego Montagner
    Date Deposited: 31 Mar 2016 15:14
    Journal or Publication Title: Inorganic Chemistry
    Publisher: American Chemical Society
    Refereed: Yes
    URI:

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