Low coordinate magnesium sulfide and selenide complexes

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

doi:10.1021/acs.inorgchem.3c02132

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

Research output: Contribution to journal › Article › peer-review

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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.

Original language	English
Pages (from-to)	16443-16450
Number of pages	8
Journal	Inorganic Chemistry
Volume	62
Issue number	40
Early online date	25 Sept 2023
DOIs	https://doi.org/10.1021/acs.inorgchem.3c02132
Publication status	Published - 9 Oct 2023

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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/.
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Low Coordinate Magnesium Sulfide and Selenide Complexes (dataset)
Burnett, S. (Creator), Ferns Dsouza, R. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator), van Mourik, T. (Creator) & Stasch, A. (Creator), University of St Andrews, 26 Sept 2023
DOI: 10.17630/dd27cd97-6132-444d-9749-aa548dd8c7d8
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@article{0b8f39338d4b4e65bff3ecd786db7ca0,

title = "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.",

author = "Stuart Burnett and Rochelle Ferns and Cordes, {David B.} and Slawin, {Alexandra M. Z.} and {van Mourik}, Tanja and Andreas Stasch",

note = "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.",

year = "2023",

month = oct,

day = "9",

doi = "10.1021/acs.inorgchem.3c02132",

language = "English",

volume = "62",

pages = "16443--16450",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society (ACS)",

number = "40",

}

TY - JOUR

T1 - Low coordinate magnesium sulfide and selenide complexes

AU - Burnett, Stuart

AU - Ferns, Rochelle

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - van Mourik, Tanja

AU - Stasch, Andreas

N1 - 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.

PY - 2023/10/9

Y1 - 2023/10/9

N2 - 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.

AB - 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.

U2 - 10.1021/acs.inorgchem.3c02132

DO - 10.1021/acs.inorgchem.3c02132

M3 - Article

SN - 0020-1669

VL - 62

SP - 16443

EP - 16450

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 40

ER -

Low coordinate magnesium sulfide and selenide complexes

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Low Coordinate Magnesium Sulfide and Selenide Complexes (dataset)

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