The consecutive addition of AgSO3CF3 (1 or 2 equiv) and cyanoguanidine (1 or 2 equiv, respectively) to the platinum(II) precursor [Ptl(2)(tmeda)] leads to the cis-[Ptl(tmeda){(N) under bar CN=C(NH2)(2))](SO3CF3) (1 center dot(SO3CF3)) or cis-[Pt(tmeda){(N) under bar CN=C(NH2)(2)}(2)](SO3CF3)(2) (2 center dot(SO3CF3)(2)) complexes. The reaction between 1 center dot(SO3CF3) or 2 center dot(SO3CF3)(2) and the excess of R2NH (R = H, R-2 = C5H10) in EtOH gives the triazapentadiene compounds cis-[Pt(tmeda)((N) under bar HC(NR2)NC(NH2)(N) under barH}](SO3CF3) (3 center dot(SO3CF3) and 4 center dot(SO3CF3), correspondingly). Protonation of these species results in cis-[Pt(tmeda){(N) under bar HC(NR2)NHC(NH2)(N) under barH}](SO3CF3)(2) ([3 center dot H](SO3CF3)(2) and [4 center dot H](SO3CF3)(2), respectively). The interaction of solid 2 center dot(SO3CF3)(2) and the gaseous RNH2 (R = H, Me) leads to cis-[Pt(tmeda){(N) under bar HC(NHR)NHC(NH2)NH}(2)](SO3CF3)(2) (5 center dot(SO3CF3)(2) and 6 center dot(SO3CF3)(2), respectively). Treatment of an acetone solution of 2 center dot(SO3CF3)(2) with an aqueous NH3 or the reaction of 5 center dot(SO3CF3)(2) with Me2CO produces the triazine complex cis-Pt(tmeda){(N) under barH=CNHC(Me)(2)}NHC(NH)(2)N}(2)(SO3CF3)(2) (7 center dot(SO3CF3)(2)). The reaction of 5 center dot(SO3CF3)(2) with Me2CO also leads to 7 center dot(SO3CF3)(2). All new complexes were characterized by elemental analyses (C, H, N), electrospray ionization mass spectrometry, IR, and H-1 and C-13 NMR spectroscopies. The structures of 1 center dot(SO3CF3), 2 center dot(SO3CF3)(2), 3 center dot(SO3CF3), [4 center dot H](SO3CF3)(2), 5 center dot(SO3CF3)(2), and 7 center dot(SO3CF3)(2) were determined by single-crystal X-ray diffraction.