| Abstract
| - The synthesis and reactivity of new Pt(II) complexes, including anionic d8 complexes, based on the electron-rich, hemilabile PNN-type pincer ligand C5H3N-2-(CH2PtBu2)(CH2NEt2) are described. Formation of these complexes involves dearomatization/aromatization processes of the ligand. The chloride complex [(PNN)PtCl]+Cl− (1) was prepared and reacted with the base tBuOK to give the deprotonated, neutral chloride complex (PNN*)PtCl (2) (PNN* = C5H3N-2-(CHPtBu2)(CH2NEt2)). Reaction of 2 with nBuLi gave the corresponding neutral hydride complex (PNN*)PtH (3), which was readily protonated by triflic acid to give the cationic hydride complex [(PNN)PtH]+OTf− (4). Unexpectedly, reaction of complex 2 with 1 equiv of RLi resulted in opening of the chelate ring, to give the corresponding anionic, dearomatized complexes Li+[(PNN*)Pt(Cl)(R)]− (R = methyl, 5; phenyl, 6). Notably, these complexes are relatively stable although they bear no stabilizing π acceptors that can lower the electron density at the metal center. Complexes 5 and 6 readily undergo protonation by HCl to form the corresponding neutral, aromatic complexes (PNN)Pt(Cl)(R) (R = methyl, 7; phenyl, 8), in which the hemilabile amine “arm” remains decoordinated and does not undergo protonation. Minor amounts of the dearomatized chloride complex 2 are also formed as a result of elimination of RH. Reaction of complexes 5 and 6 with water results in selective protonation−aromatization to give the corresponding complexes 7 and 8.
- The PNN ligand takes an active role in the formation and reactivity of Pt(II) cationic, neutral, and anionic complexes, by virtue of dearomatization/ aromatization processes and hemilability. Nucleophilic attack by RLi on the charge-neutral, dearomatized (PNN*)Pt−Cl does not result in Cl substitution; rather, anionic highly electron-rich d8 complexes are formed, as a result of amine “arm” opening, possibly assisted by Li+ coordination.
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