Tetryl-Tetrylene Addition to Phenylacetylene.

Phenylacetylene adds [Ar*GeH -SnAr'], [Ar*GeH -PbAr'] and [Ar'SnH -PbAr*] at rt in a regioselective and stereoselective reaction. The highest reactivity was found for the stannylene, which reacts immediately upon addition of one equivalent of alkyne. However, the plumbylenes exhibit addition to the alkyne only in reaction with an excess of phenylacetylene.

Hydridoorganostannylene Coordination: Group 4 Metallocene Dichloride Reduction in Reaction with Organodihydridostannate Anions.

Organodihydridoelement anions of germanium and tin were reacted with metallocene dichlorides of Group 4 metals Ti, Zr and Hf. The germate anion [Ar*GeH ] reacts with hafnocene dichloride under formation of the substitution product [Cp Hf(GeH Ar*) ]. Reaction of the organodihydridostannate with metallocene dichlorides affords the reduction products [Cp M(SnHAr*) ] (M=Ti, Zr, Hf).

Deprotonation of Organogermanium and Organotin Trihydrides.

Terphenyltin and terphenylgermanium trihydrides were deprotonated in reaction with strong bases, such as LiMe, LDA, or KBn. In the solid state, the Li salts of the germate anion and exhibit a Li-Ge contact. In the Li salt of the dihydridostannate anion , the Li cation is not coordinated at the tin atom instead an interaction of the Li cation with the hydride substituents was found.

Reductive Elimination of Hydrogen from Bis(trimethylsilyl)methyltin Trihydride and Mesityltin Trihydride.

Alkyltin trihydride [(Me Si) CHSnH ] was synthesized and the reductive elimination of hydrogen from this species was investigated. A methyl-substituted N-heterocyclic carbene reacts with the organotrihydride in dependence on stoichiometry and solvent to give a series of products of the reductive elimination and dehydrogenative tin-tin bond formation. Besides characterization of the carbene adduct of the alkyltin(II) hydride, a Sn chain was also isolated, encompassing two stannyl-stannylene sites, which are stabilized each as NHC-adducts.