Group 13 metal carbochalcogenoato complexes: Synthesis, X‐ray structure analysis, and reactions

Abstract

A series of alkali metal tetrakis(carbochalcogenoato)‐gallates and ‐indates M[M′(EOCR)4](solv.) (M = alkali metal; M′ = Ga, In; E = S, Se) and tris(carbodithioato)aluminum, ‐gallates and ‐indates M′ (SSCR)3 (M′ = Al, Ga, In) were prepared by the reactions of alkali metal carbochalcogenate with metal trihalogenides (M′X3; M′ = Al, Ga, In; X = Cl, Br) and by those of piperidinium carbodithioates or carbodithioic and carboselenoic acids with M′X3, respectively. An X‐ray molecular structure analysis revealed that they have an acetone molecule as a crystal solvent. The reactions of the potassium complexes K[M′ (EOCR)4](H2O) (E = S, Se) with methanol and primary and secondary amines gave the corresponding methyl ester and amides in good yields, while the reactions with iodomethane and iodine gave S‐ and Se‐methyl chalcogenoesters RCOEMe (E = S, Se) in good yields. Similar reactions of the tris(carbodithioato)gallates and ‐indates led to the corresponding O‐methyl thioesters, thioamides, and S‐methyl dithioesters in moderate to good yields. Oxidation of the tetrakis‐ and tris‐derivatives with iodine afforded the corresponding diacyl dichalcogenides (RCOE)2 (E = S, Se) and di(carbothioyl) disulfides in quantitative yields. These reactions appeared to occur on the carbonyl or selenium atom of the tetrakis compounds and on the sulfide sulfur or thiocarbonyl carbon atom of the tris‐compounds, respectively. A possible mechanism for these I2‐oxidation reactions is discussed.

Structural and Dynamic Properties of Gallium Alkoxides

“…Previously, we have investigated the stepwise route to alkyl/chloro-gallium donor-functionalized alkoxides from the reactions of gallium chloride with lithium dimethylamide and lithium hexamethyldisilazide, including an in-depth crystal structure analysis. Other works report of functionalization through ethers, and more recently, even thioethers to deposit oxysulfide thin films. , Gallium/copper mixed-metal thiolate compounds, used for potential gallium copper sulfide materials, were shown to have simple room-temperature NMR spectra; however, low-temperature NMR studies revealed the complex dissociative mechanisms that these precursors undergo in solution. This information can be used to understand thermolytic pathways during deposition to the target material.…”