Solubilizing functionalized molecular aluminosilicates

Abstract

Molecular aluminosilicate Al(SH)(micro-O)Si(OH)(O(t)Bu)(2) ( = [HC{C(Me)N(Ar)}(2)](-), Ar = 2,6-(i)Pr(2)C(6)H(3)) has been prepared from Al(SH)(2) and ((t)BuO)(2)Si(OH)(2) in high yield. When reacted with one equiv. of water, the unique aluminosilicate containing two terminal hydroxy groups Al(OH.THF)(mu-O)Si(OH)(O(t)Bu)(2) can be isolated. However, when is reacted with the bulkier silanol ((t)BuO)(3)SiOH, no reaction is observed. The desired Al(SH)(micro-O)Si(O(t)Bu)(3) can be prepared in a two-step synthesis between AlH(2) and ((t)BuO)(3)SiOH giving first Al(H)(micro-O)Si(O(t)Bu)(3), which reacts further with elemental sulfur to give as the only product. Direct hydrolysis of was conducted to obtain Al(OH)(micro-O)Si(O(t)Bu)(3), however, such hydrolysis always resulted in a complete decomposition of the starting material. Therefore we used boric acid, which condenses in non-polar solvents and slowly evolve water, to hydrolyze to under mild conditions. Compounds , and have been characterized by single-crystal X-ray diffraction.

β‐Diketiminate Gallium Amides: Useful Synthons in Gallium Chemistry

“…It is noteworthy that compound 8 is the first gallium compound containing two terminal ethoxy groups. Up to now, only [{(Me 3 Si) 3 Si}(EtO)Ga(µ-OEt)] 2 , [22] [(tBuO)HGa(µ-OtBu)] 2 , [23] Ga(OtBu) 3 NHMe 2 , [24] Ga[(µ-OiPr) 2 Ga(OiPr) 2 ] 3 , [24] Ga[OCH(CF 3 ) 2 ] 3 (4-Me 2 Npy) (py = pyridine), [25] Ga[OCMe 2 CF 3 ] 3 (4-Me 2 Npy), [25] and [Ga(µ-OCMe 2 Et)(OCMe 2 Et) 2 ] 2 [24] have been reported to contain at least one terminal alkoxide group. The only other compounds containing nonbridging Ga-O(alkyl) bonds are stabilized against oligomerization by the presence of donor groups that fill vacant coordination sites of the gallium atom and can lead to an increase in the coordination number for gallium to 5 or 6.…”

“…[30] Nevertheless, they are slightly longer or comparable to the terminal Ga-O(alkyl) bonds in [{(Me 3 Si) 3 Si}(EtO)Ga(µ-OEt)] 2 [1.785(7) Å], [22] [(tBuO)HGa(µ-OtBu)] 2 [1.782(5) Å], [23] Ga(OtBu) 3 NHMe 2 [1.799(2)-1.822(2) Å], [24] Ga[(µ-OiPr) 2 Ga(OiPr) 2 ] 3 (av. 1.805 Å, only bonds without disorder), [24] [24] and LGa(OH) 2 [1.777(1)-1.820(1) Å], [8] but shorter than those in (iPrO)Ga(S 2 CNEt 2 ) 2 [1.932(1) Å] [33] and in LGa(µ-O) 2 -GaL [1.848(1) and 1.854(1) Å].…”

“…[1][2][3] Thus, we became interested in whether or not it was possible to obtain similar systems based on gallium. However, whereas LAlH 2 [4] and LAl(SH) 2 , [5] used as the starting materials for the aluminophosphite and aluminosilicates, are easily accessible precursors, there are very few suitable equivalents available in gallium chemistry.…”

“…[18] and one terminal N(H)SiMe 3 group was reported in Cl 2 Ga(THF)N(H)SiMe 3 . [19] Herein we want to report on the preparation of four gallium diamide compounds of general formula LGa(NHR) 2 and LAl(NHEt) 2 , two compounds of general formula LGa(NHR)Cl, and the alcoholysis products LGa(OEt) 2 and LGa(OEt)Cl.…”

“…-) and LAl(Z)(µ-O)Si(OtBu) 3 , (Z = H, OH, SH) and their use for the preparation of heterobimetallic systems. [1][2][3] Thus, we became interested in whether or not it was possible to obtain similar systems based on gallium.…”