The Uracil C(5) Position as a Metal Binding Site: Solution and X-ray Crystal Structure Studies of Pt(II) and Hg(II) Compounds.
1,3-Dimethyluracil (1,3-DimeU) reacts with trans-[(CH(3)NH(2))(2)Pt(H(2)O)(2)](+) to give trans-[(CH(3)NH(2))(2)Pt(1,3-DimeU-C5)(H(2)O)]X (X = NO(3)(-), 1a, ClO(4)(-), 1b) and subsequently with NaCl to give trans-(CH(3)NH(2))(2)Pt(1,3-DimeU-C5)Cl (2) or with NH(3) to yield trans-[(CH(3)NH(2))(2)Pt(1,3-DimeU-C5)(NH(3))]ClO(4) (3). In a similar way, (dien)Pt(II) forms [dienPt(1,3-DimeU-C5)](+) (4). Reactions leading to formation of 1 and 4 are slow, taking days. In contrast, Hg(CH(3)COO)(2) reacts fast with 1,3-DimeU to give (1,3-DimeU-C5)Hg(CH(3)COO) (5). Both 1-methyluracil (1-MeUH) and uridine (urdH) react with (dien)Pt(II) initially at N(3) and subsequently with either (dien)Pt(II) or Hg(CH(3)COO)(2) also at C(5) to give the diplatinated species 7 and 9 or the mixed PtHg complex 8. C(5) binding of either Pt(II) or Hg(II) is evident from coupling of uracil-H(6) with either (195)Pt or (199)Hg nuclei and (3)J values of 47-74 Hz (for Pt compounds) and 185-197 Hz (for Hg compounds). J values of Pt compounds are influenced both by the ligands trans to the uracil C(5) position and by the number of metal entities bound to a uracil ring. Both 2 and 5 were X-ray structurally characterized. 2: monoclinic system, space group P2(1)/c, a = 15.736(6) Å, b = 11.481(6) Å, c = 25.655 (10) Å, beta = 145.55(3) degrees, V = 2621.9(28) Å(3), Z = 4. 5: monoclinic system, space group P2(1)/c, a = 4.905(2) Å, b = 18.451(6) Å, c = 11.801(5) Å, beta = 94.47(3) degrees, V = 1064.77(72) Å(3), Z = 4.
Höpp
Markus
M
Fachbereich Chemie, Universität Dortmund, 44221 Dortmund, Germany.
Erxleben
Andrea
A
Rombeck
Ingo
I
Lippert
Bernhard
B