Reductive Elimination and Oxidative Addition of Hydrogen at Organostannylium and Organogermylium Cations

Abstract

Bulkily substituted organodihydrogermylium and ‐stannylium cations [Ar*EH2]+ (E=Ge, Sn; Ar*=2,6‐Trip2C6H3, Trip=2,4,6‐triisopropylphenyl) were characterized as salts of the weakly coordinating perfluorinated alkoxyaluminate anion [Al{OC(CF3)3}4]−. At room temperature, the stannylium cation liberates hydrogen to generate the low valent organotin cation [Ar*Sn]+. In contrast, the dihydrogermylium cation transfers the hydrogen atoms to an aryl moiety of the terphenyl ligand and oxidatively adds either hydrogen under an atmosphere of hydrogen or a sp2 CH unit of the 1,2‐difluorobenzene solvent.

Hydridotetrylene [Ar*EH] (E = Ge, Sn, Pb) coordination at tantalum, tungsten, and zirconium

“…Low valent hydrides of tin and lead [(Ar*EH)2] (E = Sn, Pb) [47][48][49] as crystalline material (L = solvent benzene). 37,39,[47][48][49][50][51] Dissolved in 1,2-difluorobenzene (o-DFB) the cations were reacted with one equivalent of a toluene solution of tantalocene trihydride Cp2TaH3. In the case of the tin cation a product was selectively formed (Scheme 2) and in the lead case a mixture of undefined reaction products was obtained.…”

Tetryl‐Tetrylene Addition to Phenylacetylene

“…In the solid state the tin atom exhibits contacts to C5 and C9 which are manifested by a decrease of the angle Sn‐C1‐C6 to 106.5(2)° and interatomic distances of Sn−C5 2.765(2), Sn−C9 3.054(2) Å. This type of interaction was also discussed for the cation [Ar*Sn(C 6 H 6 )] + [26] …”

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me3P)2(Ph3P)Rh≡E‐Ar*] (E=Sn, Pb)

“…The base induced reductive elimination of hydrogen was investigated [9a–c, 10] . Chemistry of cationic hydrides was explored after hydride abstraction from organoelement trihydrides [9d, 11] . Deprotonation of trihydrides yields the highly reactive organoelement dihydrido anions of germanium and tin [9e,f] .…”