摘要 : The tridentate dianionic ligand 2-[2'-(hydroxyisopropoxyphos-phoryl)phenylsulfanyl]benzoate(L~(2-))reacts with cis-[Pt(NH3)2(H2O)2]~(2+)to form an S,O-chelate in which the O-co-ordinated group is either carboxylate or phosphonate,... 展开 The tridentate dianionic ligand 2-[2'-(hydroxyisopropoxyphos-phoryl)phenylsulfanyl]benzoate(L~(2-))reacts with cis-[Pt(NH3)2(H2O)2]~(2+)to form an S,O-chelate in which the O-co-ordinated group is either carboxylate or phosphonate,depending on the degree of protonation of the complex.Carboxylate appears to be the stronger ligand,and the stoichiometric reaction between cis-[Pt(NH3)2(H2O)2]~(2+)and L~(2-)yields the neutral species [Pt(L)-(NH3)2],with L bound by sulfanyl and carboxylate groups,both in solution and in the solid state.Upon protonation of [Pt(L)(NH3)2],the stronger basicity of the carboxylate causes the Pt coordination to switch from carboxylate to phosphonate,and the uncoordinated carboxylate group becomes pro-tonated.In methanolic solution,the first-order kinetics of this rearrange- ment could be observed by ~(31)P NMR spectroscopy.Both complexes-the car- boxylate-bound neutral complex [Pt(L)(NH3)2]·H2O(triclinic,P1 (no.2),a = 9.529(6),b = 9.766(6),c = 12.299(7)A,alpha = 106.91(2),beta = 101.71(2),gamma = 102.05(2)°,Z=2)and the perchlorate salt of the phosphonate- bound complex [Pt(LH)-(NH3)2]ClO_4 ·H2O(monoclinic,PZ_1/c(no.14),a = 12.095(2),b = 14.046(2),c= 14.448(2)A,beta = 95.55(2)°,Z=4)- were characterized by X-ray crystallography. 收起