1050381-21-9Relevant articles and documents
Organouranium complexes with phosphinine-based SPS pincer ligands. Variations with the substituent at the phosphorus atom
Arliguie, Therese,Blug, Matthias,Le Floch, Pascal,Mezailles, Nicolas,Thuery, Pierre,Ephritikhine, Michel
, p. 4158 - 4165 (2008)
Reaction of [K(Et2O)] [SPSMe] with [U(Cp*)(BH4)3] or [U(COT)(BH4) 2(THF)] in THF gave the expected substitution products [U(Cp*)(BH4)2(SPSMe)] (1) and [U(COT)(BH4)(SPSMe)] (2), respectively. Protonolysis of 2 with [NEt3H][BPh4] afforded the cationic complex [U(COT)(SPSMe)(NEt3)][BPh4] (3), which was transformed into [U(COT)(SPSMe)(L)][BPh4] [L = OPPh 3 (4) or HMPA (5)]. Changing [K(Et2O)] [SPS OMe1] with [Na][SPSOMe] in its reaction with [U(COT)(BH4)2(THF)] afforded a mixture of complexes, among which [U(COT)(BH4)(SPSH)] (6) was deposited as red crystals of a THF solvate. Complex 6 was isolated in 79% yield from the reaction of [U(COT)(BH4)2(THF)] and SPS in the presence of a catalytic amount of NaBH4; the key intermediate of the reaction is [Na(THF)x] [SPSH · BH3], formed by addition of NaBH4 to SPS, which reacts with [U(COT)(BH 4)2(THF)] to give 6 and NaBH4. The X-ray crystal structures of 1 · 4.5C6H12, 2 ·THF, 5 ?Et2O, and 6 ? 1.5THF indicate that the central moiety of the SPS ligand can be considered as a classical phosphine, the anionic charge being stabilized by delocalization over the five carbon atoms of the phosphahexadienyl anion and negative hyperconjugation into the two Ph 2PS pendant arms. TheX-raycrystal structures of [(U(COT)(S 2PP2)(μ-OMe)}2] and [{U(COT)}4 {U(THF)3}2(μ3-S)8], which resulted from decomposition of the SPS ligand, are also presented.
