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.
Citation
Burnett , S , Ferns , R , Cordes , D B , Slawin , A M Z , van Mourik , T & Stasch , A 2023 , ' Low coordinate magnesium sulfide and selenide complexes ' , Inorganic Chemistry , vol. 62 , no. 40 , pp. 16443-16450 . https://doi.org/10.1021/acs.inorgchem.3c02132
Publication
Inorganic Chemistry
Status
Peer reviewed
ISSN
0020-1669Type
Journal article
Rights
Copyright © 2023 The Authors. Published by American Chemical Society. This Open Access publication is licensed under a Creative Commons Attribution 4.0 International licence (CC-BY 4.0). To view licence visit: https://creativecommons.org/licenses/by/4.0/.
Description
Funding: Authors thank the University of St Andrews and the EPSRC doctoral training grant (EP/N509759/1) for support. We gratefully acknowledge computational support via the EaStCHEM Research Computing Facility.Collections
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