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. Complete dehydrogenation resulted to give either a carbene-stabilized distannyne or a metalloid Sn -cluster salt. Reductive elimination of hydrogen was also achieved with an excess of diethylmethylamine to give the alkyltin(II) hydride as a Lewis base free tetramer [(RSnH) ]. The method of cluster formation at low temperatures by hydrogen elimination was also transferred to the mesityl-substituted tin trihydride MesSnH . In this case [(MesSn) ], showing a [5]prismane structure, was isolated in good yield and characterized. NMR spectroscopic features of the propellane-type cluster [Trip Sn ] are reported.

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 4 and 4a exhibit a Li–Ge contact. In the Li salt of the dihydridostannate anion 6a, the Li cation is not coordinated at the tin atom instead an interaction of the Li cation with the hydride substituents was found. Evidenced by 1H–7Li-HOESY NMR spectroscopy the Li-salt of the deprotonated tin hydride 6a exhibits in toluene solution a contact between Li cation and hydride substituents, whereas in the 1H–7Li-HOESY NMR spectrum of the homologous germate salt 4a, no crosspeak between hydride and Li signals was found. The organodihydridogermate and -stannate react as nucleophiles with low-valent Group 14 electrophiles. Thus, three compounds were synthesized: Ar–Ë′–EH2–Ar (E′, E = Sn, Ge; Pb, Ge; Pb, Sn; Ar = Ar′, Ar*). Following an alternative synthesis Ar′SnH2PbAr* was synthesized in reaction between [(Ar*PbH)2] and [(Ar′SnH)4] generated in situ. In reaction between low-valent organotin hydride [(Ar*SnH)2] and organdihydridostannate [Ar*SnH2]− formation of distannate [Ar*2Sn2H3]− was found.

Organodihydridoelement anions of germanium and tin were reacted with metallocene dichlorides of Group 4 metals Ti, Zr and Hf. The germate anion [Ar*GeH2]− reacts with hafnocene dichloride under formation of the substitution product [Cp2Hf(GeH2Ar*)2]. Reaction of the organodihydridostannate with metallocene dichlorides affords the reduction products [Cp2M(SnHAr*)2] (M=Ti, Zr, Hf). Abstraction of a hydride substituent from the titanium bis(hydridoorganostannylene) complex results in formation of cation [Cp2M(SnAr*)(SnHAr*)]+ exhibiting a short Ti–Sn interaction. (Ar*=2,6‐Trip2C6H3, Trip=2,4,6‐triisopropylphenyl).

The coordination chemistry of intramolecular stannylene phosphorus Lewis pairs incorporated into four membered ring systems is presented. Previously reported coordination chemistry of stannylene and phosphorus towards palladium(0) is extended by using Pd(nbe) as a precursor, yielding co-ligand free complexes. An equilibrium of one or two stannylene phosphorus ligands coordinated to Pd(0) was observed with tin acting either as a donor or an acceptor towards palladium. Furthermore, the reactions with transition metal(i) chlorides, [(cod)IrCl], [(cod)RhCl] and MeSAuCl are reported. They proceed via insertion of stannylene into the M-Cl bonds, yielding metal complexes with chelating stannide phosphorus ligands. For gold, a dinuclear complex with bridging P-Sn ligands was formed. Furthermore, the reaction of a P → Sn Lewis pair in a three membered ring system with (cod)PtMe is reported.