Low-Coordinate Magnesium Sulfide and Selenide Complexes.

ABSTRACT: 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.

SUBMITTER: Burnett S 

PROVIDER: S-EPMC10565804 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature