Access to Base Adducts of Low‐Valent Organotin‐Hydride Compounds by Controlled, Stepwise Hydrogen Abstraction from a Tetravalent Organotin Trihydride

Abstract

Hydrogen can be selectively removed from organotin trihydrides to generate the corresponding organohydrostannylene intermediates. Depending on the size of the substituent and the mode of generation, the intermediates undergo further reactions. Herein, we report on the formation of a variety of organotin hydrides with tin in the oxidation states Sn(II) , Sn(I) -Sn(III) and Sn(III) -Sn(III) , all accessed by the controlled removal of hydrogen from the tetravalent Ar'Sn(IV) trihydride (Ar'=2,6-dimesitylphenyl, mesityl=2,4,6-trimethylphenyl).

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

“…The Hf−Sn bond lengths in hafnocene derivatives [CpCp*Hf(SnPh 3 ) L], on the other hand, are significantly longer: L=Cl, 2.9650(4); NMe 2 , 2.9694(8); Me, 2.9740(5); OMe, 2.9556(5) Å . The Sn−Sn distances [ 4 : 3.370(1), 5 : 3.526(1), 6 : 3.489(1) Å] in complexes 4 – 6 are longer than typical Sn−Sn single bonds [Ar′H 2 Sn‐SnH 2 Ar“, 2.7449(3)] [Ar′=2,6‐Mes 2 C 6 H 3 , Mes=2,4,6‐trimethylphenyl], however short enough to point towards a minor interaction between both tin atoms . Coordination of two stannylenes at metallocene fragments was previously reported in B , F and Cp 2 Zr(SnL 2 ) 2 .…”

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

“…[D 8 ]THF was distilled from LiAlD 4 and stored in a dry box. Terphenyl‐ iodide (Ar*I) ‐lithium derivative (Ar*Li(OEt 2 )),‐Sn II chloride (Ar*SnCl, Ar*GeCl), were prepared according to modified literature procedures and Sn IV trichloride (Ar*SnCl 3 ), Sn IV hydride, deuteride were prepared as previously described ,. (Ar*GeCl 3 ) was prepared according to a modified literature procedure .…”

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

“…The Sn−H stretching frequency was found at 1732 cm −1 and lies below the value for SnH 4 (1899 cm −1 ), (Me 3 Si) 2 CHSnH 3 (1864 cm −1 and a stannyl stannylene Ar′Sn( i Pr NHC)SnH 2 Ar′ (Ar′=mesityl‐terphenyl), which shows a vibration at 1778 cm −1 …”