CYTOSINE NUCLEOBASE AS A TRIDENTATE LIGAND - METAL-BINDING TO N(3), N(4) AND O(2) IN TRANS-[(NH(2)ME)(2)PT(DMCYT)(2)AG-2][NO3](2) (DMCYT=1,5-DIMETHYLCYTOSINATE)
D. Holthenrich et al., CYTOSINE NUCLEOBASE AS A TRIDENTATE LIGAND - METAL-BINDING TO N(3), N(4) AND O(2) IN TRANS-[(NH(2)ME)(2)PT(DMCYT)(2)AG-2][NO3](2) (DMCYT=1,5-DIMETHYLCYTOSINATE), Journal of the Chemical Society. Dalton transactions, (20), 1995, pp. 3275-3279
1,5-Dimethylcytosine (Hdmcyt). which is a model of the naturally occur
ring 5-methylcytidine nucleobase, has been demonstrated to be capable
of binding three metal ions simultaneously, via N(3), monodeprotonated
N(4) and O(2). The compound trans-[(NH(2)Me)(2)Pt(dmcyt)(2)Ag-2][NO3]
(2) 1 was prepared from trans-[Pt(NH(2)Me)(2)(Hdmyct-N-3)(2)] [NO3](2)
and AgNO3 at alkaline pH. and its crystal structure determined. The P
t ... Ag distances within the trinuclear cation are 2.892(1) and 3.040
(1) Angstrom. The compound is compared with related mixed Pt-Ag nucleo
base complexes as well as other trinuclear d(10)-d(8)-d(10) systems. D
espite the problem of differentiation of the nucleobase arrangement (h
ead-to-head or head-to-tail) due to the pseudo-two-fold symmetry of th
e 1,5-dimethylcytosine ligand, the head-to-head orientation has unambi
guously been established by use of H-1 NMR spectroscopy following prec
ipitation of AgCl.