The reaction between K[PtCl(3)(Me(2)SO)] or prepared in this work cis- and trans-[PtCl(2)(NCNR(2))(Me(2)SO)] (R(2) = Me(2), 1; C(4)H(8)O, 2; C(5)H(10) 3) with an excess of NCNR(2) in water gives the cationic bischelate [Pt{κ(2)-N,N'''-NH=C(NMe(2))OC(NMe(2))=NH}(2)](2+) (4(2+)) and the monochelates [PtCl{κ(2)-N,O-NH=C(NR(2))NC(NR(2))=O}(Me(2)SO)] (R(2) = C(4)H(8)O, 5; C(5)H(10), 6). Complex 4(2+) was released from the reaction mixture as 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2) or it was precipitated as 4·[A](2) (A = pic, 4·[pic](2); PF(6), 4·[PF(6)](2); BPh(4), 4·[BPh(4)](2)·(NH(2)CONMe(2))) by addition of picric acid, NaPF(6), or NaBPh(4), respectively, to the filtrate obtained after separation of 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2). In 2, the dialkylcyanamide ligand undergoes bond cleavage giving the known trans-[PtCl(2){N(H)C(4)H(8)O}(Me(2)SO)] (trans-7). All complexes were characterized by elemental analyses (C, H, N), high resolution ESI-MS, IR, (1)H and (13)C{(1)H} NMR spectroscopic techniques, including 2D NMR correlation experiments ((1)H,(1)H-COSY, (1)H,(13)C-HMQC/(1)H,(13)C HSQC, (1)H,(13)C-HMBC, and (1)H,(1)H-NOESY). The structures of cis-1, cis-3, 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2), 4·[BPh(4)](2)·(NH(2)CONMe(2)) and 5 were determined by a single-crystal X-ray diffraction.