Direct electrochemical synthesis of alkane- and arenethiolato derivatives of indium and thallium

The direct electrochemical synthesis of d10 metal ion derivatives of some anionic bidentate oxygen donors

“…The method of preparing these new compounds was essentially the same as those used in our previous papers (1)(2)(3)(4)(5)(6)(7)(8)(9)(10). The solution phase was contained in a 100 mL round-bottomed flask with a Schlenk arm; a metal rod suspended through rubber septum formed the anode of the cell, and a platinum wire was the cathode.…”

“…The isolation of the indium(II1) flavonate can be explained in terms of the initial formation of an indium(1) species electrochemically, followed by disproportionation according to the stoichiometry [4] 31n(Cl5H9O3) + 21n + In(C15H903) 3 In keeping with this argument, during the initial stages'of the electrolysis we observed the formation of a yellow solid, which quickly decomposes shortly after its formation with the deposition of metallic indium, which can be isolated in the quantity required by the stoichiometry of reaction [4].…”

The direct electrochemical synthesis of some metal derivatives of 3-hydroxy-2-methyl-4-pyrone

“…The electrochemical procedures were essentially those described in earlier papers (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11). The electrochemical cell was a 100 mL round-bottomed flask with a Schlenk arm containing the solution phase; the sacrificial metal electrode suspended by a platinum wire through the rubber septum was the anode of the cell and a second platinum wire similarly supported was the cathode.…”

“…No direct reaction between malt01 and indium metal was detected, establishing the absence of any competing chemical reaction at the anode, but we did observe that some of the metal which was thrown down in the cell during electrolysis could become mechanically reattached to the anode when the reaction mixture was shaken, and such processes may account for the observed non-reproducibility in EF. The product recovered from the solution was identified as InL,, and in terms of the known chemistry of this element, one would predict the sequence Cathode [4] HL + e -, 1/2 H2(g) + LAnode [5] In + L-+ InL + e Solr Lion phase [6] 3InL -, 2 In0 + InL3 so that the overall stoichiometry is [7] 31n + 2 In + InL3 : observed (mmol) 3.88, 1.87, 1. 5 1 In view of the experimental observations reported above, we suspect that the loss of indium from the anode is underestimated, and that the quantity of indium metal collected at the end of the experiment is also too low, partly because of adherence to the anode and partly.…”

“…A number of papers from this laboratory have demonstrated that the method of direct electrochemical synthesis is a simple, efficient one-step route to the preparation of a wide range of metal complexes, including metal thiolates (1)(2)(3)(4)(5), diphenylphosphides (6), carboxylates (7), catecholates (8,9), and dipyridylamides (10). The method consists simply in the reduction of the selected substrate at an inert platinum cathode in a non-aqueous solution, followed by the oxidation of a sacrificial metal anode.…”