Reactions of Dimethyl[tris(trimethylsilyl)methyl]metalanes of Aluminum and Gallium with H2S and Elemental Chalcogens – Crystal Structures of [RAl(μ-S)]2·2 THF, [RGa(μ3-S)]4, [{RAl(μ3-S)}3MeAl(μ3-S)], [RAlMe(μ-SeMe)]2, and [RGaMe(μ-TeMe)]2 [R = C(SiMe3)3]

Abstract

The reaction of the trialkylalane (Me3Si)3CAlMe2 × THF (1) with H2S in toluene at room temperature results in the formation of the dimeric sulfido compound [(Me3Si)3CAl(μ‐S)]2 × 2 THF (3), while the reaction of the homologous gallane (Me3Si)3CGaMe2 (2) with H2S under similar conditions affords the heterocubane [(Me3Si)3CGa(μ3‐S)]4 (4). Heating of compound 3 in vacuo gives a mixture of the symmetrically substituted [(Me3Si)3CAl(μ3‐S)]4 (5) and the unsymmetrically substituted heterocubane [{(Me3Si)3CAl(μ3‐S)}3MeAl(μ3‐S)] (6). Reaction of the trialkylmetalanes 1 and 2 with elemental selenium in refluxing toluene results in the formation of the corresponding selenolates [(Me3Si)3CMMe(μ‐SeMe)]2 (7, M = Al; 8, M = Ga). The compounds exhibit a high thermal stability and can not be converted to the corresponding selenides [(Me3Si)3CM(μ3‐Se)]n (M = Al, Ga) upon heating. In contrast, the trialkylalane 1 does not react with tellurium metal in refluxing toluene at all, while the trialkylgallane 2 affords the tellurolate [(Me3Si)3CGaMe(μ‐TeMe)]2 (9) under similar conditions. Compounds 3–9 have been characterized by 1H‐ and 29Si‐NMR, mass, and IR spectroscopy. Furthermore, the molecular structures of compounds 3· C6H6, 4· 1.5 C6H6, 6, 7· C6H6 and 9 have been determined by X‐ray crystallography.

Cyclopentadienylaluminum thiolates – synthesis and structure

“…Among these compounds aluminum alkoxides have been the most systematically and broadly examined (see for example [2]). Comparing to aluminum alkoxides the chemistry of thiolate derivatives is rather scant [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. The structures of organoaluminum thiolates are diversified and the factors controlling them are not still definitely examined.…”

Te–Te and Te–C bond cleavage reactions using a monovalent gallanediyl

“…31 The same holds for the Ga-Te bonds in four structurally characterized Ga 4 Te 4 heterocubanes, which range from 2.67 to 2.72 Å, [32][33][34][35] as well as in dimeric compounds of the general type [R 2 Ga-μ-TeR] 2 , for which Ga-Te bond lengths in the range from 2.67 to 2.76 Å were reported. [36][37][38][39] In contrast, slightly shorter Ga-Te bond lengths were reported for {[(Me 3 Si) 2 CH] 2 Ga-μ-Te} (2.5521(4) Å), 40 [(Me 3 Si) 2 CH] 2 GaTeSi(SiMe 3 ) 3 (2.535(1) Å), 41 whereas the Ga-Te bonds observed in Ga{TeSi(SiMe 3 ) 3 } 3 (av. 2.496(6) Å) 42 as well as in Tp # GaTe (2.422( 1)) (Tp # = tris(3,5-di-tert-butylpyrazolyl) hydroborato), to date the only compound containing a terminal Ga-Te double bond, are significantly shortened.…”

Organometallic compounds containing tris(trimethylsilyl)methyl or related ligands †

“…Organoaluminates of these types have hitherto been little studied even though they are related to the intermediates in the reduction of carbonyl compounds and disulfides by LiAlH Reaction of AlTsiMe 2 with H 2 S gives {AlTsi(thf)S} 2 , which on heating gives the cubane (AlTsiS) 4 31, M = Al, E = S. The gallium compound (GaTsiS) 4 can be made similarly. 138 When the chloride AlTsiCl 2 ؒthf is reduced by Na-K in thf the solvent is incorporated into the product 32; AlTsiI 2 is, however, converted cleanly into the cluster 33a, which is stable up to 282 ЊC. 139 The ability of trisyl-type groups to stabilise metals in low oxidation states has been particularly well exploited by Uhl for the preparation of compounds of the heavier Group 13 elements.…”