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Treatment of CpRuH(PP) (PP=dppm, dppe) with TlPF6 produced [CpRu(H)(Tl)(PP)]PF6. X‐ray diffraction and computational studies suggest that the complexes contain a Ru−H−Tl 3c–2e bond and can be viewed as the first σ‐complexes of period 6 main‐group hydrides [CpRu{η2‐(H−Tl)}(PP)]PF6 or [Tl{η2‐H−RuCp(PP)}]PF6. The complexes can be stored as a solid at room temperature for days without appreciable decomposition,...
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