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Coordination of W(CO)5 to DNA and RNA nucleobases: development of a possible heavy-metal labeling complex

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Abstract

Photolysis of W(CO)6 in acetone solvent in the presence of DNA/RNA nucleobases attached to their ribose sugars has revealed attachment of the W(CO)5 moiety at N-7, N-1 and N-3 for both guanosine (G) and adenosine (A). Cytidine (C) coordinates only at N-3. Thymidine (T) and uridine (U) do not coordinate via a pyrimidine site, but engage in attack at the C3′ ribose position to form a carbene. The isomer distribution of W(CO)5 to G and A follows a pattern recently discovered for RuII of [Ru(hedta)] in that the softer metal centers (compared to PtII agents) favor binding at N-3 over N-7 in a ratio close to 70:30 for RuII on G, matched by a 72:28 ratio for W(CO)5 with G and 78:22 with A where the ratio represents N-3 plus N-1 coordination : N-7 coordination for the W(CO)5 series. The results indicate the possibility of developing a water-soluble L′W(CO)4 heavy atom attachment for X-ray structural uses or as a metallo-drug wherein L′ serves as a solubilizing, trans directing agent in the photolysis of W(CO)5L′.

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Stringfield, T.W., Shepherd, R.E. Coordination of W(CO)5 to DNA and RNA nucleobases: development of a possible heavy-metal labeling complex. Transition Metal Chemistry 24, 571–576 (1999). https://doi.org/10.1023/A:1006957427199

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