Chalcogenides of aluminium(III) and gallium(III) derived from Lewis base adducts of alane and gallane

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

“…28 In addition, the mixed Te/carboxylate-bridged compound [R 2 Ga 2 (μ-Te)(μ-OOCCH 3 ) 2 ] (2.534 Å) 29 as well as the basestabilized compounds LGa(TePh) 3 (L = NMe 3 , PCy 3 ), which were obtained from the reaction of base-stabilized gallanes [LGaH 3 ] with Ph 2 Te 2 and which also contain fourfold-coordinated Ga atoms and twofold-coordinated Te atoms, show comparable Ga-Te bond distances of 2.580(1) Å and 2.597(2) Å, respectively. 30 In contrast, the Ga-Te bonds in the [MeGa (TePh) 3 ] + monocation of [(Me 3 P) 4 Cu][MeGa(TePh) 3 ] is slightly elongated (2.6406(3) Å). 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.…”

“…43 Reactions of trivalent group 13 compounds (MR 3 , MH 3 ; M = Al, Ga, In) with elemental chalcogens E or chalcogen sources such as R 3 PvE (E = O, S, Se, Te) typically occur with insertion of the chalcogen atom into the M-C/H bond and subsequent formation of dimeric ([R 2 M-μ-ER] 2 ) or tetrameric ([RME] 4 ) compounds, whereas divalent (R 4 M 2 ) as well as monovalent group 13 compounds RM (M = Al, Ga, In, Tl) react with insertion of the chalcogen atom into the M-M bond. [44][45][46][47][48][49] In addition, E-Br bond cleavage reactions of PhEBr (E = Se, Te) upon treatment with the monovalent In(I) cluster [(Me 3 Si) 3 C] 4 In 4 50 as well as of Te-Te bond cleavage reactions of Ph 2 Te 2 by reaction with Ga(I) 26 and In(I) compounds 51 as well as with base-stabilized GaH 3 30 were reported. However, to the best of our knowledge, the cleavage of the Te-C bond of diorganyltellanes upon reaction with monovalent group 13 compounds RM has never been observed before.…”

“…This journal is © The 26 and In(I) compounds 51 as well as with base-stabilized GaH 3 30 were reported. However, to the best of our knowledge, the cleavage of the Te-C bond of diorganyltellanes upon reaction with monovalent group 13 compounds RM has never been observed before.…”

The Reaction Chemistry of Aluminum(I,III) Compounds Stabilized by Sterically Bulky Ligands

“…[21] However, reactions involving aluminum hydrides of low aggregation with chalcogen or organochalcogenides have been reported to a lesser extent. Raston et al [22][23][24][25] investigated the reaction of trimethylamine adduct of alane -------------------------------------------7 Me 3 N•AlH 3 with chalcogen or organochalcogenide. Power et al [26] reported one example of the reaction of aluminum dihydride with organochalcogenide and our group discussed the reaction of a series of aluminum dihydrides with chalcogen, [21,[27][28][29][30] where the isolation and structural characterization of some novel compounds (such as LAl(SeH) 2 , LAl(SeH)Se(SeH)AlL, [21] LAl(SH) 2 [27] (L = N(Ar)C(Me)CHC(Me)N(Ar), Ar = 2,6-iPr 2 C 6 H 3 ); (RAlE) 2 (R = 2,4,6-tBu 3 C 6 H 2 , E = S; [26] R = N(SiMe 3 )C(Ph)C(SiMe 3 ) 2 , [28] 2,6-(Et 2 NCH 2 ) 2 C 6 H 3 , 2-Et 2 NCH 2 -6-MeC 6 H 3 , [29] E = Se, Te), trans-[{Me 3 N(H)Al(µ-E)} 2 ] (E = Se, Te), [23] trans-[{Me 3 N(PhTe)Al(µ-Se)} 2 ]; [24] [(η 1 -3,5-tBu 2 pz(µ-Al)H] 2 E (E = S, Se, Te); [30] Me 3 NAl(ER) 3 (E = Se, R = Et, Ph, CH 2 Ph; E = Te, R = Ph) [22] and Al 4 Se 5 (H) 2 (NMe 3 ) 4 [24] )…”

Synthesis, Structural Studies and Reactivity of Monomeric Organo Aluminum and Gallium Amides, Hydrogensulfides and Hydroxides Using N-Heterocyclic Carbene: Precursors for Heterobimetallic Systems

“…In these systems chalcogenes can act either as µ or µ 3 bridging ligand, as a consequence of the steric hindrance of the substituents present on the aluminum atoms. Thus, the (AlE) n core can be either square planar (n = 2), [42][43][44][45][46][47][48][49][50][51]55] cubic (n = 4) [51−55] or adopt a hexagonal drum structure (n = 6) (Figure 2). [52] Other examples containing Al and E in a ratio deviating from the 1:1 ratio have been reported exhibiting bent Al−E−Al, adamantane-like Al 4 E 6 or more complex structures, respectively.…”