Different routes for amination of platinum(II)-bound cyanoguanidine.

The consecutive addition of AgSO(3)CF(3) (1 or 2 equiv) and cyanoguanidine (1 or 2 equiv, respectively) to the platinum(II) precursor [PtI(2)(tmeda)] leads to the cis-[PtI(tmeda){NCN=C(NH(2))(2)}](SO(3)CF(3)) (1.(SO(3)CF(3))) or cis-[Pt(tmeda){NCN=C(NH(2))(2)}(2)](SO(3)CF(3))(2) (2.(SO(3)CF(3))(2)) complexes. The reaction between 1.(SO(3)CF(3)) or 2.(SO(3)CF(3))(2) and the excess of R(2)NH (R = H, R(2) = C(5)H(10)) in EtOH gives the triazapentadiene compounds cis-[Pt(tmeda){NHC(NR(2))NC(NH(2))NH}](SO(3)CF(3)) (3.(SO(3)CF(3)) and 4.(SO(3)CF(3)), correspondingly). Protonation of these species results in cis-[Pt(tmeda){NHC(NR(2))NHC(NH(2))NH}](SO(3)CF(3))(2) ([3.H](SO(3)CF(3))(2) and [4.H](SO(3)CF(3))(2), respectively). The interaction of solid 2.(SO(3)CF(3))(2) and the gaseous RNH(2) (R = H, Me) leads to cis-[Pt(tmeda){NHC(NHR)NHC(NH(2))NH}(2)](SO(3)CF(3))(2) (5.(SO(3)CF(3))(2) and 6.(SO(3)CF(3))(2), respectively). Treatment of an acetone solution of 2.(SO(3)CF(3))(2) with an aqueous NH(3) or the reaction of 5.(SO(3)CF(3))(2) with Me(2)CO produces the triazine complex cis-{Pt(tmeda){NH=CNHC(Me)(2)}NHC(NH)(2)N}(2)(SO(3)CF(3))(2) (7.(SO(3)CF(3))(2)). The reaction of 5.(SO(3)CF(3))(2) with Me(2)CO also leads to 7.(SO(3)CF(3))(2). All new complexes were characterized by elemental analyses (C, H, N), electrospray ionization mass spectrometry, IR, and (1)H and (13)C NMR spectroscopies. The structures of 1.(SO(3)CF(3)), 2.(SO(3)CF(3))(2), 3.(SO(3)CF(3)), [4.H](SO(3)CF(3))(2), 5.(SO(3)CF(3))(2), and 7.(SO(3)CF(3))(2) were determined by single-crystal X-ray diffraction.