The reaction of K-2[PtCl4] and HO(H)NCMe2CMe2N(H)OH center dot H2SO4 (BHA center dot H2SO4; 2) in a molar ratio 1:2 at 20-25 degrees C in water affords a mixture of [Pt(BHA)(2)][PtCl4] (5) and [Pt(BHA-H)(2)] (6) (BHA-H = anionic monodeprotonated form of BHA) which, upon heating at 80-85 degrees C for 12 h or on prolonged keeping at 20-25 degrees C for 2 weeks, is subject to a slow transformation giving [PtCl2(BHA)] (7). The latter compound is also obtained from the reaction between K[PtCl3(Me-2(S) under barO)] and 2. The chlorination of [PtCl2(BHA)] (7) in freshly distilled dry chloroform leads to the selective oxidation of one N(H)OH group yielding [PtCl2{HO(H)(M) under bar CMe2CMe2(N) under bar =O}] (13), while the chlorination in water produces the complex [PtCl2(O=(N) under bar CMe2CMe2N=O)] (14) bearing the unexplored dinitrosoalkane species. Treatment of 14 with 2 equiv of 1,2-bis-(diphenylphosphino)ethane (dppe) in CH2Cl2 results in the liberation of the dinitrosoalkane ligand followed by its fast cyclization giving the alpha-dinitrone (3,3,4,4-tetramethyl -1,2-diazete-1,2 dioxide) in solution and the solid [Pt(dpp(e))(2)](Cl)(2). The Pt-II complexes with hydroxylaminol(boolean AND)oximes [PtCl2{HO(H)(N) under barC(Me)(2)C(R)=(N) under bar OH)] (R = Me 8; R = Ph 9) upon their oxidation with Cl-2 in CHCl3 afford the nitrosoalkane derivatives [PtCl2{O=(N) under bar CMe2C(R)=(N) under bar OH}] (R = Me 16; Ph 17), respectively, while the corresponding chlorination of the bis-chelates [Pt{HO(H)(N) under bar CMe2C(R)=(N) under bar OH}(2)] (R = Me 10; Ph 11) gives [Pt{O=(N) under bar CMe2C(R)=(N) under barO}(2)] (R = Me 18; Ph 19). The formulation of 5-19 is based on C, H, and N microanalyses, IR, 1D (H-1, C-13{H-1}), (195)pt) and 2D (H-1,H-1-COSY,H-1,C-13-HSQC) NMR spectroscopies, and X-ray diffraction for five complexes (5, 7, and 12-14).