1388649-96-4Relevant articles and documents
Two-electron redox chemistry at the dinuclear core of a TePt platform: Chlorine photoreductive elimination and isolation of a TeVPt I complex
Lin, Tzu-Pin,Gabbai, Francois P.
, p. 12230 - 12238 (2012/09/11)
As part of our interest in novel redox-active main group/transition metal platforms for energy applications, we have synthesized the chloride salt of [TeIIIPtICl(o-dppp)2]+ ([1] +, o-dppp = o-(Ph2P)C6H4) by reaction of the new bis(phosphino) telluroether (o-(Ph2P)C 6H4)2Te with (Et2S) 2PtCl2. Complex [1]+ is chemically robust and undergoes a clean two-electron oxidation reaction in the presence of PhICl 2 to afford ClTeIIIPtIIICl3(o-dppp) 2 (2), a complex combining a hypervalent four-coordinate tellurium atom and an octahedral platinum center. While the Te-Pt bond length is only slightly affected by the oxidation state of the TePt platform, DFT and NBO calculations show that this central linkage undergoes an umpolung from Te→Pt in [1]+ to Te←Pt in 2. This umpolung signals an increase in the electron releasing ability of the tellurium center upon switching from an eight-electron configuration in [1]+ to a hypervalent configuration in 2. Remarkably, the two-electron redox chemistry displayed by this new dinuclear platform is reversible as shown by the photoreductive elimination of a Cl2 equivalent when 2 is irradiated at 350 nm in the presence of a radical trap such as 2,3-dimethyl-1,3-butadiene. This photoreductive elimination, which affords [1][Cl] with a maximum quantum yield of 4.4%, shows that main group/late transition metal complexes can mimic the behavior of their transition metal-only analogues and, in particular, undergo halogen photoelimination from the oxidized state. A last notable outcome of this study is the isolation and characterization of F(MeO) 2TeVPtICl(o-dppp)2 (4), the first metalated hexavalent tellurium compound, which is formed by reaction of 2 with KF in the presence of MeOH.
