Condition-Driven Selective Syntheses of Dialkyl Diselenides Involving Elemental Selenium and Sodium Borohydride

Abstract

Dialkyl diselenides have been prepared from alkyl ­halides, sodium borohydride and elemental selenium using two ­different methods. One of them involves the intermediate formation of diselenide dianion equivalent (^-SeSe^-).

elemental selenium - sodium borohydride - alkylation - alkyl halides - benzyl halides - dimetal diselenide

References

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13b

Synthesized by protonation (formic acid, 2.5-4 equiv) of selenide dianion equivalent [from elemental selenium, NaBH₄ and EtOH (1:2:6) in DMF]. [13a]

14

Typically mixing elemental selenium, NaBH₄ and EtOH (1:1:3 molar equiv each) leads to the evolvement of dihydrogen (2.58 molar equiv, 86% of the expected amount), sequential addition of DMF and decyl bromide produces an additional formation of hydrogen (0.42 molar equiv, 14% of the expected amount).

15 We have been unable to determine the structure of these species by ⁷⁷Se NMR. For a related work see: Cusik J. Dance I. Polyhedron  1991,  10:  2629 

16a

in fact, we found in a control experiment that 6 molar equiv of dihydrogen escape from the medium (experimentally 97% of this amount) on reaction of selenium, NaBH₄ and EtOH (1:2:6 mol equiv).

16b

Another 0.81 molar equiv of dihydrogen is evolved if aq EtOH (4 molar equiv each), is added before that of the second crop of elemental selenium.

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