Synthesis of Cobalt‐Tin and ‐Lead Tetrylidynes—Reactivity Study of the Triple Bond
Maximilian Auer, Kathrin Zwettler, Klaus Eichele, Hartmut Schubert, Christian P. Sindlinger, Lars Wesemann
Abstract
Abstract Tetrylidynes [TbbSn≡Co(PMe 3 ) 3 ] ( 1 a ) and [TbbPb≡Co(PMe 3 ) 3 ] ( 2 ) (Tbb=2,6‐[CH(SiMe 3 ) 2 ] 2 ‐4‐( t ‐Bu)C 6 H 2 ) are accessed for the first time via a substitution reaction between [Na(OEt 2 )][Co(PMe 3 ) 4 ] and [Li(thf) 2 ][TbbEBr 2 ] (E=Sn, Pb). Following an alternative procedure the stannylidyne [Ar*Sn≡Co(PMe 3 ) 3 ] ( 1 b ) was synthesized by hydrogen atom abstraction using AIBN from the paramagnetic hydride complex [Ar*SnH=Co(PMe 3 ) 3 ] ( 4 ) (AIBN=azobis(isobutyronitrile)). The stannylidyne 1 a adds two equivalents of water to yield the dihydroxide [TbbSn(OH) 2 CoH 2 (PMe 3 ) 3 ] ( 5 ). In reaction of the stannylidyne 1 a with CO 2 a product of a redox reaction [TbbSn(CO 3 )Co(CO)(PMe 3 ) 3 ] ( 6 ) was isolated. Protonation of the tetrylidynes occurs at the cobalt atom to give the metalla‐stanna vinyl cation [TbbSn=CoH(PMe 3 ) 3 ][BAr F 4 ] ( 7 a ) [Ar F =C 6 H 3 ‐3,5‐(CF 3 ) 2 ]. The analogous germanium and tin cations [Ar*E=CoH(PMe 3 ) 3 ][BAr F 4 ] (E=Ge 9 , Sn 7 b ) (Ar*=C 6 H 3 (2,6‐Trip) 2 , Trip=2,4,6‐C 6 H 2 i Pr 3 ) were also obtained by oxidation of the paramagnetic complexes [Ar*EH=Co(PMe 3 ) 3 ] (E=Ge 3 , Sn 4 ), which were synthesized by substitution of a PMe 3 ligand of [Co(PMe 3 ) 4 ] by a hydridoylene (Ar*EH) unit.