Low coordinate magnesium sulfide and selenide complexes

Stuart Burnett, Rochelle Ferns, David B. Cordes, Alexandra M. Z. Slawin, Tanja van Mourik, Andreas Stasch*

*Corresponding author for this work

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The reactions of [{(iPrDipNacNac)Mg}2] 1 (iPrDipnacnac = HC(iPrCNDip)2) with Ph3P═O at 100 °C afforded the phosphinate complex [(iPrDipNacNac)Mg(OPPh3)(OPPh2)] 3. Reactions of 1 with Ph3P═E (E = S, Se) proceeded rapidly at room temperature to low-coordinate chalcogenide complexes [{(iPrDipNacNac)Mg}2(μ-S)] 4 and [{(iPrDipNacNac)Mg}2(μ-Se)] 5, respectively. Similarly, reactions of RNHC═S ((MeCNR)2C═S with R = Me, Et, or iPr) with 1 afforded NHC adducts of magnesium sulfide complexes, [{(iPrDipNacNac)Mg(RNHC)}(μ-S){Mg(iPrDipNacNac)}] 6, that could alternatively be obtained by adding the appropriate RNHC to sulfide complex 4. Complex 4 reacted with 1-adamantylazide (AdN3) to give [{(iPrDipNacNac)Mg}2(μ-SN3Ad)] 7 and can form various simple donor adducts in solution, of which [(iPrDipNacNac)Mg(OAd)}2(μ-S)] 8a (OAd = 2-adamantanone) was structurally characterized. The nature of the ionic Mg–E–Mg unit is described by solution and solid-state studies of the complexes and by DFT computational investigations.
Original languageEnglish
Pages (from-to)16443-16450
Number of pages8
JournalInorganic Chemistry
Issue number40
Early online date25 Sept 2023
Publication statusPublished - 9 Oct 2023


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