Molecular Ln(III)-H-E(II) Linkages (Ln=Y, Lu; E=Ge, Sn, Pb).

Following the alkane-elimination route, the reaction between tetravalent aryl tintrihydride Ar*SnH and trivalent rare-earth-metallocene alkyls [Cp* Ln(CH{SiMe } )] gave complexes [Cp* Ln(μ-H) SnAr*] implementing a low-valent tin hydride (Ln=Y, Lu; Ar*=2,6-Trip C H , Trip=2,4,6-triisopropylphenyl). The homologous complexes of germanium and lead, [Cp* Ln(μ-H) EAr*] (E = Ge, Pb), were accessed via addition of low-valent [(Ar*EH) ] to the rare-earth-metal hydrides [(Cp* LnH) ]. The lead compounds [Cp* Ln(μ-H) PbAr*] exhibit H/D exchange in reactions with deuterated solvents or dihydrogen.

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

In a reaction of tantalocene trihydride with the low valent aryl tin cation [Ar*Sn(CH)][Al(OC{CF})] (1a) the hydridostannylene complex [CpTaH-Sn(H)Ar*][Al(OC{CF})] (2) was synthesized. Hydride bridged adducts [CpWHEAr*][Al(OC{CF})] (E = Sn 3a, Pb 3b) were isolated as products of the reaction between CpWH and cations [Ar*E(CH)][Al(OC{CF})] (E = Sn 1a, Pb 1b). The tin adduct 3a exhibits a proton migration to give the hydridostannylene complex [CpW(H)[double bond, length as m-dash]Sn(H)Ar*][Al(OC{CF})] 4a.

Low valent lead and tin hydrides in reactions with heteroallenes.

Low valent organoelement hydrides of tin and lead, [(Ar*SnH)] and [(Ar*PbH)], were reacted with diorganocarbodiimide and adamantylisocyanate to give products of hydroelementation reactions. Carbon dioxide also reacts with both low valent hydrides, but a reaction product was only characterized in the tin hydride case. A hydride was transferred to the carbon atom and the formed formate anion [HCO] shows coordination at two tin atoms.

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me P) (Ph P)Rh≡E-Ar*] (E=Sn, Pb).

Tetrylidynes [(Me P) (Ph P)Rh≡SnAr*] (10) and [(Me P) (Ph P)Rh≡PbAr*] (11) are accessed for the first time via dehydrogenation of dihydrides [(Ph P) RhH SnAr*] (3) and [(Ph P) RhH PbAr*] (7) (Ar*=2,6-Trip C H , Trip=2,4,6-triisopropylphenyl), respectively. Tin dihydride 3 was either synthesized in reaction of the dihydridostannate [Ar*SnH ] with [(Ph P) RhCl] or via reaction between hydrides [(Ph P) RhH] and  [(Ar*SnH) ]. Homologous lead hydride [(Ph P) RhH PbAr*] (7) was synthesized analogously from [(Ph P) RhH] and  [(Ar*PbH) ].

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.