Synthesis and structures of monomeric group 14 triols and their reactivity

Abstract

The first stable stannanetriol and germanetriol bearing sterically congested aryl groups were synthesized by hydrolysis of the corresponding trichloro-stannane and -germane. The stannanetriol is monomeric in solution as well as in the crystalline state, as evidenced by X-ray diffraction analysis and CP-MAS NMR spectroscopy. The stannanetriol reacted with silicone grease to afford a cagelike compound having three Sn–O–Si–O–Sn linkages in the molecule. All the group 14 triols can be converted to the corresponding trihalo compounds in good yields.

Triple bonds of niobium with silicon, germaniun and tin: the tetrylidyne complexes [(κ3-tmps)(CO)2NbE–R] (E = Si, Ge, Sn; tmps = MeSi(CH2PMe2)3; R = aryl)

“…Benzene extraction of the orange-brown solid obtained after solvent evaporation afforded a benzene soluble, pale-orange part containing mainly the germanediol Ge(Ar Mes )H(OH) 2 , as well as a benzene-insoluble brownish part. The unprecedented hydridogermanediol 29 was isolated as a pale yellow solid and characterized by IR and 1 H NMR spectroscopy. Its IR spectrum displays two ν (OH) bands at 3600 and 3398 cm –1 and a characteristic ν (Ge–H) band at 2104 cm –1 , the latter one appearing at a close position to that of GeBr 2 HMes ( ν (Ge–H) = 2105 cm –1 ).…”

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

“…[7b,c, 31] (Ar*GeCl 3 )w as prepared according to am odified literature procedure. [32] [Ph 3 C] [Al(OC{CF 3 } 3 ) 4 ]w as synthesized following literature procedures. [8a] [Ph 3 C][B(C 6 F 5 ) 4 ]w as purchased from Aldrich and stored in ag lovebox.…”

Serendipitous reactions involving a silicone grease

“…(Tip = 2,4,6-triisopropylphenyl) 12a was treated with a catalytic amount of sodium hydroxide in acetone/H 2 O under reflux for a week using standard glassware with silicone grease to serendipitously afford cage-like compound 13a having three Sn O Si O Sn linkages in 12% yield (Scheme 4) [19]. As expected, deliberate addition of silicone grease into the reaction vessel increased the yield of 13a up to 43%.…”