An Unknown Coordination Mode of the Phosphite Unit and a Carbon-Free Heterocycle in Two Different Heterobimetallic Alumophosphites

Abstract

The unique alumophosphite reagent LAl(SH)(mu-O)P(OEt)2 was prepared and used for the synthesis of the heterobimetallic alumophosphites [{kappa2-S,P-LAl(S)(mu-O)P(OEt)2}2Zn] and [{kappa4-S,O,O-LAl(SLi)(mu-O)P(OEt)2}2]. The first contains a rare example of two carbon-free five-membered heterocycles (Al-S-Zn-P-O) connected in a spiro fashion through the zinc atom, whereas the second possesses an unknown example of a coordination environment of a phosphite unit M-O-P(mu-OEt)2M with an uncoordinated lone electron pair on the phosphorus center.

Solubilizing functionalized molecular aluminosilicates

“…Compounds 1, 3 and 5-7 were isolated as crystalline and stable solids. The formation of the products was confirmed by MS-EI, where the parent ions were observed at m/z 684 (1), 668 (3), 708 (5), 740 (6) and 724 (7). In addition, the [M -X] + fragment was observed at m/z 651 in compounds 1 ([M -SH] + ) and 3 ([M -OH] + ), whereas for 6 ([M -SH] + ) and 7 ([M -OH] + ), it was observed at m/z 707.…”

“…5 Recently, we have reported the preparation of aluminum silicate and phosphite precursors LAl(SH)(m-O)Si(OH)(O t Bu) 2 (1) (L = [HC{C(Me)N(Ar)} 2 ] -, Ar = 2,6-i Pr 2 C 6 H 3 ) and LAl(SH)(m-O)P(OEt) 2 from LAl(SH) 2 (2) and ( t BuO) 2 Si(OH) 2 or HP(O)(OEt) 2 , respectively, together with the corresponding lithium salts [LAl(SLi)(m-O)Si(OLi•2THF)(O t Bu) 2 ] 2 and LAl(SLi)(m-O)P(OEt) 2 ] 2 . 6,7 The controlled hydrolysis of 1 led to a molecular aluminosilicate-hydroxide LAl(OH•THF)(m-O)Si(OH)(O t Bu) 2 (3) (Scheme 1). It is known that the compound LAl(OH) 2 is labile and decomposes easily, but the presence of an Al-(m-O)-M (M = metal) bridge can stabilize the terminal OH group attached to the aluminum atom.…”

β‐Diketiminate Gallium Amides: Useful Synthons in Gallium Chemistry

“…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]. [9] Furthermore, the Ga-Cl bond lengths found for 5 [2.200 (1) [11] In all nine compounds, the coordination sphere around the central metal has a distorted tetrahedral geometry, where the N endo -M-N endo (1)(2)(3)(4)(5)(6) Table 1.…”

“…The isomorphous compounds 1 and 7 and compound 8 crystallize in the monoclinic space group P2 1 /n with one molecule in the asymmetric unit. Of the remaining compounds, the following also crystallize in the monoclinic system (the corresponding space group and asymmetric unit content are given in the parenthesis): compound 2 (P2 1 , one molecule), compound 3 (P2 1 . The values for the Ga-N exo bonds are in general smaller than the sum of the covalent radii for gallium and nitrogen (1.90 Å), [30] which is probably a result of the higher ionic contribution of these bonds.…”

“…[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.…”