57255-84-2Relevant academic research and scientific papers
Oxidation of Pt-bound bis-hydroxylamine as a novel route to unexplored dinitrosoalkane ligated species
Luzyanin, Konstantin V.,Gushchin, Pavel V.,Pombeiro, Armando J. L.,Haukka, Matti,Ovcharenko, Victor I.,Kukushkin, Vadim Yu.
, p. 6919 - 6930 (2008)
The reaction of K2[PtCl4] and HO(H)NCMe 2CMe2N(H)OH·H2SO4 (BHA·H2SO4; 2) in a molar ratio 1:2 at 20-25° 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°C for 12 h or on prolonged keeping at 20-25°C for 2 weeks, is subject to a slow transformation giving [PtCl 2(BHA)] (7). The latter compound is also obtained from the reaction between K[PtCl3(Me2Scombining minus sign belowO)] 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)Ncombining minus sign belowCMe2CMe 2N=O}] (13), while the chlorination in water produces the complex [PtCl2(O=Ncombining minus sign belowCMe2CMe 2Ncombining minus sign below=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 α-dinitrone (3,3,4,4-tetramethyl-1,2-diazete-1,2-dioxide) in solution and the solid [Pt(dppe)2](Cl)2. The PtII complexes with hydroxylamino∩oximes [PtCl2{HO(H)Ncombining minus sign belowC(Me)2C(R)=Ncombining minus sign belowOH}] (R = Me 8; R = Ph 9) upon their oxidation with Cl2 in CHCl3 afford the nitrosoalkane derivatives [PtCl2{O=Ncombining minus sign belowCMe2C(R)=Ncombining minus sign belowOH}] (R = Me 16; Ph 17), respectively, while the corresponding chlorination of the bis-chelates [Pt{HO(H)Ncombining minus sign belowCMe2C(R)=Ncombining minus sign belowOH}2] (R = Me 10; Ph 11) gives [Pt{O=Ncombining minus sign belowCMe2C(R)=Ncombining minus sign belowO}2] (R = Me 18; Ph 19). The formulation of 5-19 is based on C, H, and N microanalyses, IR, 1D (1H, 13C{1H}, 195Pt) and 2D ( 1H,1H-COSY,1H,13C-HSQC) NMR spectroscopies, and X-ray diffraction for five complexes (5, 7, and 12-14).
