The direct electrochemical synthesis of thiolato complexes of cobalt and nickel, and the crystal structure of bis(phenylthiolato)bis(1,10-phenanthroline)cobalt(III) perchlorate

Abstract

Cobalt(II) and nickel(II) thiolates, M(SR)2, can be prepared in high yield by the electrochemical oxidation of a metal anode in an acetonitrile or acetone solution of RSH (R = C6H5, o-CH3C6H4, 2-C10H7, 2,3,4,5-C6F4H; not all combinations). When 2,2-bipyridine or 1,10-phenanthroline (=L) is added to the electrolyte phase, the products are the adducts M(SR)2L2. In the case of Co(SC6H5)2(phen)2, aerial oxidation leads to the formation of the cobalt(III) cation [Co(SC6H5)2(phen)2]+, isolated as the perchlorate salt. X-ray crystallographic analysis showed that this cation has a cis-CoS2(N2)2 kernel.

Cobalt(II) and Cobalt(III) Tri-tert-butoxysilanethiolates. Synthesis, Properties, Crystal and Molecular Structures of [Co{μ-SSi(OBut)3}{SSi(OBut)3}(NH3)]2 and [Co{SSi(OBut)3}2(NH3)4][SSi(OBut)3] Complexes

“…The perchlorates of bis(phenylthiolato)bis(1,10-phenanthroline)cobalt(III) [36] and {tris(2-aminoethyl)-amine-N,N'N@}-bis(thioacetato)cobalt(III) [37] are also known. In all cases listed above, at least amine ligands are chelating.…”

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.…”

The direct electrochemical synthesis of phenylselenolato complexes of some main group and late transition elements

“…A number of papers from this laboratory have described the synthesis of M(SR), compounds by the electrochemical oxidation of a sacrificial anode in a non-aqueous solution of either a thiol or a disulphide (1)(2)(3)(4)(5)(6)). The present paper shows that these techniques can be extended to the one-step high yield synthesis of phenylselenolato complexes M(SePh),, , and in some cases, their adducts with neutral donor ligands.…”