Ligand Functionalization, Reactivity, and Transformation at the Selenide Centers of [Pt2(-Se)2(PPh3)<
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文摘
The selenium centers of [Pt2(-Se)2(PPh3)4] are subject to electrophilic attack from variousorganic halides. Reactions with MeI, n-BuCl, chars/alpha.gif" BORDER=0>,chars/alpha.gif" BORDER=0>'-dichloro-p-xylene, and chars/alpha.gif" BORDER=0>,chars/alpha.gif" BORDER=0>'-dichloro-o-xylenegive [Pt2(-Se)(-SeMe)(PPh3)4]+, [Pt2(-Se)(-SeBu)(PPh3)4]+, [Pt2(-Se)(-SeCH2C6H4CH2Cl)(PPh3)4]+, and [Pt2(-SeCH2C6H4CH2Se)(PPh3)4]2+, respectively, preserving the dinuclearcore and giving rise to new selenium-derivatized ligand complexes. Reaction with oxalylchloride gives [Pt(chars/eta.gif" BORDER=0 >2-Se2C2O2-Se,Se')(PPh3)2], leading to the disintegration of the core to amononuclear complex supported by a new chelating selenium donor ligand. Reactions withmalonyl chloride and succinyl chloride give [(COCH2COCl)Se]2 and [(COCH2CH2COCl)Se]2respectively, leading to complex disintegration and liberation of new selenium materials.The crystal structures of the aggregates [Pt2(-Se)(-SeMe)(PPh3)4][PF6], [Pt2(3-Se)2(PPh3)4(CH2C6H4CH2)][PF6]1.25[Cl]0.75, and [Pt(chars/eta.gif" BORDER=0 >2-Se2C2O2-Se,Se')(PPh3)2] are described. The potentialof using [Pt2(-Se)2(PPh3)4] as a source for metal-assisted synthesis of new and unusualorganoselenium compounds is discussed.

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