Adducts of fac-[Re(CO)3(H2O)3]+ with 5'- and 3'-guanosine monophosphate investigated in aqueous solution by multinuclear NMR spectroscopy

INOR 626

Kristie M. Adams, kadams9@lsu.edu and Luigi G. Marzilli, lmarzil@lsu.edu. Department of Chemistry, Louisiana State University, Room 232 Choppin Hall, Baton Rouge, LA 70810
The fac-[Re(I)(CO)3(H2O)3]+ cation is the putative reactive species binding to DNA, the likely biomolecular target responsible for anticancer activity of related Re(I) compounds. In dilute aqueous solution 5'-guanosine monophosphate (5'-GMP) added to fac-[Re(I)(CO)3(H2O)3]+ slightly faster than 3'-guanosine monophosphate (3'-GMP) to form a 1:1 Re:GMP adduct. This adduct formed the 1:2 adduct faster for 3'-GMP than for 5'-GMP. We can also establish that 1:2 3'-GMP adducts are thermodynamically more favored than 1:2 5'-GMP adducts. A ternary mixture experiment (5'-GMP:3'-GMP:Re) excluded the formation of 2:2 cyclic dimers or macrochelates; however, the data revealed the formation of two mixed 5'-GMP/3'-GMP bis adducts in a 60:40 ratio. At equilibrium, the mixed adducts are less stable than the 3'-GMP bis adduct but more stable than the 5'-GMP bis adduct. The phosphate group cannot approach the metal for 3'-GMP; the greater stability for the 3'-GMP adducts probably reflects more favorable N1H-phosphate interligand interactions for 3'-GMP vs. 5'-GMP.
 

Bioinorganic Chemistry
7:00 PM-10:00 PM, Tuesday, 12 September 2006 Moscone Center -- Hall D, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, 11 September 2006 Moscone Center -- Hall D, Sci-Mix

Division of Inorganic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006