A homoleptic SPS-based complex and a double-cubane-type sulfur cluster of an actinide element

Treatment of UI3(THF)4 with [M(Et2O)][SPSMe] (M = Li, K; [SPSMe]− = 1-methyl-2,6-bis(diphenylphosphine sulfide)-3,5-diphenylphosphinine anion) gave the cationic tris SPS complex [U(SPSMe)3]I (1). Similar reaction of U(BH4)3(THF)3 and [M(Et2O)][SPSMe] afforded, in addition to the [U(SPS)3]+ cation, crystals of the sulfido complex [U{(μ3-S)4U3(SPSMe)3(BH4)3}2] (2). The metal environment in 1 is a tricapped trigonal prism and the core of the heptanuclear cluster 2 is a corner-shared double-cubane.

Treatment of UI3(THF)4 with [M(Et2O)][SPSMe] (M = Li, K; [SPSMe]− = 1-methyl-2,6-bis(diphenylphosphine sulfide)-3,5-diphenylphosphinine anion) gave the tris SPS complex [U(SPSMe)3]I which adopts a tricapped trigonal prismatic configuration. Similar reaction of U(BH4)3(THF)3 afforded, in addition to the [U(SPS)3]+ cation, crystals of the heptanuclear sulfido cluster [U{(μ3-S)4U3(SPSMe)3(BH4)3}2] which exhibits a corner-shared double-cubane core.Figure optionsDownload as PowerPoint slide