Reactions of Digallanes with p‐ and d‐Block Lewis Bases: Adducts, Bis(gallyl) Complexes, and Naked Ga⁺ as Ligand

Abstract

A range of double carbene adducts of digallanes(4) are prepared from an existing double digallane adduct, and their halides are subsequently exchanged, establishing the feasibility of both base and halide-exchange reactions from digallane adducts. Furthermore, a range of digallium species are treated with transition-metal Lewis bases, leading alternatively to oxidative addition products, species with monocoordinate Ga ligands, and an unusual ditopic metal-only Lewis pair (MOLP). These results underline the manifold and unpredictable chemistry of halogallane species with Lewis bases.

Cyclic (Alkyl)(Amino)Carbene-Stabilized Aluminum and Gallium Radicals Based on Amidinate Scaffolds

“…2 shows a significantly shortened gallium−carbene bond distance [1.9342( 17) Å] compared to the digallane (cAAC) 2 Ga 2 Cl 4 [2.078(2) Å]. 20 The same holds true for the Ga−Cl bond [2, 2.1952(5) Å; (cAAC) 2 Ga 2 Cl 4 , 2.257(1) and 2.229(1) Å].…”

“…The carbene aluminum bond [ 1 , 1.9355(13) Å] is significantly shorter than those in (cAAC) 2 AlCl 2 [1.967(2) and 2.097(2) Å] and (cAAC) 2 AlEtCl [1.9913(13) and 2.1507(13) Å] complexes. 2 shows a significantly shortened gallium–carbene bond distance [1.9342(17) Å] compared to the digallane (cAAC) 2 Ga 2 Cl 4 [2.078(2) Å] . The same holds true for the Ga–Cl bond [ 2 , 2.1952(5) Å; (cAAC) 2 Ga 2 Cl 4 , 2.257(1) and 2.229(1) Å].…”

Insights into the Composition and Structural Chemistry of Gallium(I) Triflate

“…[Ga(arene) n ] + salts catalyze the polymerization of alkenes, [5e,f, 6] and have been shown to be active catalysts for cycloisomerization, transfer hydrogenation, and reductive hydroarylation reactions [9] . There is also evidence for Ga I involvement in important mechanistic steps that underpin many catalytic reactions, for example, reductive elimination, suggesting exciting possibilities for the Ga I /Ga III redox couple in other catalytic reactions [3c, 6] . In related work, the use of Ga 0 in synthesis and materials chemistry has received attention [10]…”

Synthesis and redox activity of carbene-coordinated group 13 metal radicals

“…13 b ,20 Comparable findings were observed for cation 6 , showing a longer Ga–C cAAC bond (2.037(1) Å) than radical 4 (1.932(3) Å), whereas comparable bond lengths were reported for (cAAC)GaCl 3 (2.039(2) Å), 16 (cAAC)GaHCl 2 (2.053(2) Å), 19 and (cAAC) 2 Ga 2 Cl 4 (2.078(2) Å), respectively. 21 The M–C IPr bonds (2.047(1) 5 ; 2.026(1) Å 6 ) are slightly shorter than those of neutral radicals 3 (2.078(1) Å) and 4 (2.059(3) Å), but still fall in the typical range of Al–C IPr and Ga–C IPr bond lengths. 11,15,17–20…”