Reactivity of organogermanium and organotin trihydrides

Abstract

The organogermanium and organotin trihydrides (TbbEH3) [E = Ge (3), Sn (7)] with the Tbb substituent were synthesized by hydride substitution (Tbb = 2,6-[CH(SiMe3)2]2-4-(t-Bu)C6H2). Deprotonation of the organoelement trihydrides 3...

Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH3, N2H4, H2O, H2)

“…30 In our initial efforts we reacted low valent organo element bromides of germanium [(TbbGeBr) 2 ] and tin [TbbSnBr 2 ][Li(thf) 2 ] with the iridium hydride [(Me 3 P) 4 IrH] (Scheme 3 and Table 1). 31,32,33 A phosphine was substituted against the bromoorgano tetrylene and the tetrylidene compounds [(TbbBrE)IrH(PMe 3 ) 3 ] (E = Ge: 1 , E = Sn: 2 , see Scheme 3 for depiction) were obtained in high yield ( 1 : 96%, 2 : 95%). In the case of the germanium derivative 1 , determination of the molecular structure in the solid state was possible (see Table 2 and ESI† for details).…”

“…30 In our initial efforts we reacted low valent organo element bromides of germanium [(TbbGeBr) 2 ] and tin [TbbSnBr 2 ][Li(thf) 2 ] with the iridium hydride [(Me 3 P) 4 IrH] (Scheme 3 and Table 1). 31,32,33 A phosphine was substituted against the bromoorgano tetrylene and the tetrylidene compounds [(TbbBrE)IrH(PMe 3 ) 3 ] (E = Ge:…”

“…An irido-stannylene ( 18) is formed, which was also synthesized with varying phosphines (18-PMe 3 , 19-PEt 3 ) by an alternative approach starting from the trihydride TbbSnH 3 (Scheme 6). 33 Deprotonation using benzyl-potassium yields [TbbSnH 2 K] and is followed by reaction with the electrophile [(R 3 P) n IrCl] (R = Me n = 4, R = Et n = 3). 121,122 During this synthesis of complexes 18 and 19, two hydrogen atoms show a 1,2-H shi from tin to iridium.…”

Isolation and Reactivity of Stannylenoids Stabilized by Amido/Imino Ligands

“…[19] More recently, Wesemann and coworkers described the complex [TbbSnBr 2 ][Li(THF) 2 ] (Tbb = 2,6-[CH(SiMe 3 ) 2 ] 2 -4-t BuC 6 H 2 ) containing a four-membered LiBr 2 Sn ring. [20] Motivated by the above results, we report on a room temperature stable stannylenoid by using a bulky amido ligand. We also show its facile transformations into the corresponding amidostannylenes.…”

“…In 2016, we reported a rare example of a lithium stannylenoid J prepared by using the N‐heterocyclic imine (NHI) ligand and verified the high stannylenoid character of this compound by demonstrating its ambiphilic reactivity [19] . More recently, Wesemann and coworkers described the complex [TbbSnBr 2 ][Li(THF) 2 ] (Tbb=2,6‐[CH(SiMe 3 ) 2 ] 2 ‐4‐ t BuC 6 H 2 ) containing a four‐membered LiBr 2 Sn ring [20] …”