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Luzyanin KV, Gushchin PV, Pombeiro AJ, Haukka M, Ovcharenko VI, Kukushkin VY: Oxidation of Pt-bound bis-hydroxylamine as a novel route to unexplored dinitrosoalkane ligated species. Inorg Chem. 2008 Aug 4;47(15):6919-30. Epub 2008 Jun 27.
The reaction of K 2 [PtCl 4] and HO (H) NCMe 2CMe 2N (H) OH.H 2SO 4 ( BHA.H 2SO 4; 2) in a molar ratio 1:2 at 20-25 degrees C in water affords a mixture of [Pt (BHA) 2][PtCl 4] ( 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 [PtCl 2 (BHA)] ( 7). The latter compound is also obtained from the reaction between K [PtCl 3 (Me 2 SO)] and 2. The chlorination of [PtCl 2 (BHA)] ( 7) in freshly distilled dry chloroform leads to the selective oxidation of one N (H) OH group yielding [PtCl 2{HO (H) NCMe 2CMe 2 N=O}] ( 13), while the chlorination in water produces the complex [PtCl 2 (O= NCMe 2CMe 2 N=O)] ( 14) bearing the unexplored dinitrosoalkane species. Treatment of 14 with 2 equiv of 1,2-bis-(diphenylphosphino) ethane (dppe) in CH 2Cl 2 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 (dppe) 2](Cl) 2. The Pt (II) complexes with hydroxylamino ( intersection) oximes [PtCl 2{HO (H) NC (Me) 2C (R)= NOH}] (R = Me 8; R = Ph 9) upon their oxidation with Cl 2 in CHCl 3 afford the nitrosoalkane derivatives [PtCl 2{O= NCMe 2C (R)= NOH}] (R = Me 16; Ph 17), respectively, while the corresponding chlorination of the bis-chelates [Pt{HO (H) NCMe 2C (R)= NOH} 2] (R = Me 10; Ph 11) gives [Pt{O= NCMe 2C (R)= NO} 2] (R = Me 18; Ph 19). The formulation of 5- 19 is based on C, H, and N microanalyses, IR, 1D ( (1) H, (13) C{ (1) H}, (195) Pt) and 2D ( (1) H, (1) H-COSY, (1) H, (13) C-HSQC) NMR spectroscopies, and X-ray diffraction for five complexes ( 5, 7, and 12- 14). |
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