Reactivity of Organoelement Subhalides of Gallium and Indium — Ga−Ga and In−In Bonds Bridged by Carboxylato Ligands

Abstract

The organoelement subhalides R2Ga2I2 (5) and R3In3I2 [6; R = C(SiMe3)3] reacted with silver benzoate AgOOCC6H5 to yield the dicarboxylato dielement compounds R2E2(µ‐OOCC6H5‐O,O′)2 (7, E = Ga; 8, E = In). Both compounds possess E−E single bonds bridged by the chelating carboxylato ligands. The chelating groups are arranged perpendicular to one another. Owing to the small bite of the carboxylato group very short E−E bond lengths of 240.5 pm (Ga−Ga) and 265.4 pm (In−In) were observed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

“Crowned” Univalent Indium Complexes as Donors? Experimental and Computational Insights on the Valence Isomers of EE′X4 Species

“…It should be emphasized that these crystal structures confirm that the donor-acceptor valence isomeric form illustrated in Figure 2 c that we had initially observed for "InCl 2 " is not anomalous and is indeed viable for the heavier dihalides InBr 2 and InI 2 . The InÀIn bond lengths are found to range from 2.6726(7) and 2.725 (2) and are on the shorter end of the values reported (2.654 [35] -3.197 [36] ) in the Cambridge Structural Database (CSD); [37] most of these reported distances are for covalent diindane variants that have been reviewed previously. [38][39][40][41] It is worth noting that the InÀIn distances in 3-5 increase as the halogen atom becomes heavier; such an observation is consistent with the decreasing Lewis acidity of the InX 3 as X changed from Cl to Br to I.…”

1,4‐Di(isopropyl)‐1,4‐diazabutadien als Abfangreagenz für monomere Bruchstücke des Tetragalliumclusters Ga4[C(SiMe3)3]4 – Bildung eines ungesättigten GaN2C2‐Heterocyclus und eines Oxidationsprodukts mit Ga‐O‐O‐Ga‐Gruppe

“…Nur in einem Fall, In 4 SR 4 , gelang der Transfer eines einzigen Chalkogenatoms unter Erhalt der tetraedrischen Anordnung der vier niederwertigen Indiumatome [8]. In jüngster Zeit beschäftigten wir uns intensiv mit der Synthese von Halogenderivaten der Cluster, die als Ausgangsverbindungen zur Darstellung neuartiger Folgeprodukte mit den Elementen Gallium und Indium in ungewöhnlicher Oxidationsstufe besonderes Interesse verdienen [9]. Die Oxidation mit den Halogenen oder mit Halogendonoren führte zur Bildung von drei unterschiedlichen Strukturmotiven, die sich anhand der Oxidationsstufen der Zentralatome unterscheiden lassen.…”

Investigations into the Reactivity of Organoelement Gallium Subhalides – Syntheses of Bifunctional Digallium Carboxylate Iodides Possessing Bridged Ga–Ga Bonds and Terminal Iodine Atoms

“…Ga2 has an almost ideal planar surrounding (sum of the angles 358.5 and 357.2° for 2 and 4 , respectively), while Ga1 has a strongly distorted tetrahedral coordination sphere. The Ga–Ga bond lengths (239.9 and 240.7 pm) are quite similar to that of the starting compound 1 (240.1 pm)4 and to the corresponding dicarboxylato derivative, in which two chelating ligands bridge the Ga–Ga bond 11,17. However, they are shorter than the unsupported Ga–Ga bonds of tetraalkyl or tetraaryl digallium compounds (>260 pm,18 for a review see ref 5…”

“…The replacement of both iodine atoms of the subhalide I 2 Ga 2 R 2 ( 1 ) [R = C(SiMe 3 ) 3 ] by carboxylato groups resulted in reasonable yields and reaction times only when silver benzoate was employed as a starting compound,11 while lithium benzoate gave complicated mixtures of products. However, it seems that only the exchange of the second iodine atom is relatively slow and unselective.…”

“…The chelating ligands occupy terminal positions at each gallium or indium atom. In contrast, the bridging of the E–E bonds was observed for dicarboxylato compounds 11. A very short E–E distance resulted in particular for the indium derivative owing to the small bite of the carboxylato group.…”