Synthesis of Cobalt‐Tin and ‐Lead Tetrylidynes—Reactivity Study of the Triple Bond

Tetrylidynes [TbbSn≡Co(PMe3)3] (1 a) and [TbbPb≡Co(PMe3)3] (2) (Tbb=2,6‐[CH(SiMe3)2]2‐4‐(t‐Bu)C6H2) are accessed for the first time via a substitution reaction between [Na(OEt2)][Co(PMe3)4] and [Li(thf)2][TbbEBr2] (E=Sn, Pb). Following an alternative procedure the stannylidyne [Ar*Sn≡Co(PMe3)3] (1 b) was synthesized by hydrogen atom ion using AIBN from the paramagnetic hydride complex [Ar*SnH=Co(PMe3)3] (4) (AIBN=azobis(isobutyronitrile)). The stannylidyne 1 a adds two equivalents of water to yield the dihydroxide [TbbSn(OH)2CoH2(PMe3)3] (5). In reaction of the stannylidyne 1 a with CO2 a product of a redox reaction [TbbSn(CO3)Co(CO)(PMe3)3] (6) was isolated. Protonation of the tetrylidynes occurs at the cobalt atom to give the metalla‐stanna vinyl cation [TbbSn=CoH(PMe3)3][BArF4] (7 a) [ArF=C6H3‐3,5‐(CF3)2]. The analogous germanium and tin cations [Ar*E=CoH(PMe3)3][BArF4] (E=Ge 9, Sn 7 b) (Ar*=C6H3(2,6‐Trip)2, Trip=2,4,6‐C6H2iPr3) were also obtained by oxidation of the paramagnetic complexes [Ar*EH=Co(PMe3)3] (E=Ge 3, Sn 4), which were synthesized by substitution of a PMe3 ligand of [Co(PMe3)4] by a hydridoylene (Ar*EH) unit. Tetrylidynes featuring a triple bond between cobalt and tin or lead have been synthesized via a substitution reaction between anionic cobalt complex [Co(PMe3)4]− and halides of tin and lead. The cobalt stannylidyne adds two equivalents of water to give a cobalt dihydride moiety and tin dihydroxide unit. In reaction with carbon dioxide the stannylidyne forms a cobalt carbonyl complex featuring a carbonate ligand coordinated at tin.