950767-98-3Relevant academic research and scientific papers
Alkyl carbon-nitrogen reductive elimination from platinum(IV)-sulfonamide complexes
Pawlikowski, Andrew V.,Getty, April D.,Goldberg, Karen I.
, p. 10382 - 10393 (2008/02/12)
Platinum(IV) complexes containing monodentate sulfonamide ligands, fac-(dppbz)PtMe3(NHSO2R) (dppbz = o-bis(diphenylphosphino) benzene; R = p-C6H4(CH2)3CH 3 (1a), p-C6H4CH3 (1b), CH 3 (1c)), have been synthesized and characterized, and their thermal reactivity has been explored. Compounds 1a-c undergo competitive C-N and C-C reductive elimination upon thermolysis to form N-methylsulfonamides and ethane, respectively. Selectivity for either C-N or C-C bond formation can be achieved by altering the reaction conditions. Good yields of the C-N-coupled products were observed when the thermolyses of 1a-c were conducted in benzene-d 6. In contrast, exclusive C-C reductive elimination occurred upon thermolysis of 1a,b in nitrobenzene-d5. When the thermolyses of 1a were performed in the presence of sulfonamide anion NHSO2R - in benzene-d6, ethane elimination was completely inhibited and C-N reductive elimination products were formed in high yield. Mechanistic studies support a two-step reaction pathway involving initial dissociation of NHSO2R- from the platinum center, followed by nucleophilic attack of this anion on a methyl group of the resulting five-coordinate platinum(IV) cation to form MeNHSO2R and (dppbz)-PtMe2. C-C reductive elimination to form ethane occurs directly from the five-coordinate Pt(IV) cation.
