Inorganic Chemistry, Vol.33, No.18, 4149-4158, 1994
Atropisomerization of Cis-bis(5’gmp)-Platinum(II)-Diamine Complexes with Non-C2-Symmetrical Asymmetric Diamine Ligands Containing NH Groups Directed to One Side of the Coordination Plane
Complexes of the type LPt(5’GMP)2, where L = N,N’-dimethyl-2,3-diaminobutane and the stereochemistries at the four asymmetric centers (N, C, C, N) are S,R,R,R and S,S,S,R, were prepared at pH 3.5 from the respective LPt(SO4) compounds by treating with 2 equiv of 5’GMP. These complexes have both diamine NH groups directed to the same side of the coordination plane. The resulting 5’GMP complexes were studied by using 1D and 2D NMR methods. NOE data demonstrate that the 5’GMPs are coordinated via N7 to two nonequivalent Pt coordination sites. Restricted rotation about the Pt-N7 bonds potentially could lead to four different atropisomers for each complex : two head-to-tail (HT) and two head-to-head (HH) species with the H8s of the 5’GMP on the opposite side and on the same side of the Pt coordination plane, respectively. Four atropisomers would exhibit a total of eight H8 signals. : two head-to-tail (HT) and two head-to-head (HH) species with the H8s of the 5’GMP on the opposite side and on the same side of the Pt coordination plane, respectively. Four atropisomers would exhibit a total of eight H8 signals.
Keywords:PLATINUM ANTICANCER COMPLEXES;NUCLEAR-MAGNETIC-RESONANCE;INTRASTRAND CROSS-LINKING;ANTI-CANCER ACTIVITY;DRUG CIS-DIAMMINEDICHLOROPLATINUM(II);BONDING INTERACTIONS;MOLECULAR-STRUCTURE;MODEL COMPOUNDS;DNA;ADDUCTS