Platinum complexes have been synthesized containing tris(1-phenyl-1H-1,2,3,-triazol 4-yl)phosphine oxide (TtPh), a tristriazolyl phosphine oxide scorpionate ligand. Metallation of this neutral tridentate ligand using [(�-SMe2)Pt(CH3)2]2 or [(�-SEt2)Pt(C6H5)2]2 results in the corresponding  square planar Pt(II) complexes with a ?2 coordination mode, similar to that of trispyrazolylmethane systems. Treatment of the ?2 complexes with alkyl or allyl electrophiles results in oxidation of the metal center and generation of Pt(IV) cations of the type [?3-TtPhPt(R)2(R')][X] (R=Me or Ph; R'=Me, Et, nPr, s-CH2CHCH2, or s-CH2C(CH3)CH2; X=OTf or I).Protonation of ?2-TtPhPt(CH3)2 results in a cationic dimethyl hydride species, [?3-TtPhPt(CH3)2(H)][X] (X=OTf or BAr4F). Thermolysis of this complex at 35�C in the presence of a trapping ligand results in elimination of methane and formation of a Pt(II) complex of the type [TtPhPt(CH3)(L)][X] (L=CO, ethylene, propylene, cis-2-butylene, trans-2-butylene, or isobutylene; X=OTf or BAr4F). The weakly donating TtPh ligand undergoes dechelation and subsequent trapping under significantly milder conditions than the well-studied Tp'Pt(CH3)(H) complex which requires thermolysis at temperatures above 100�C.

Synthesis, characterization, and reactivity of platinum phospha-scorpionate complexes

239th National Meeting (2010)

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