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Systematics of boron halide complexes with dichalcogenoether ligands – synthesis, structures and reaction chemistry

Systematics of boron halide complexes with dichalcogenoether ligands – synthesis, structures and reaction chemistry
Systematics of boron halide complexes with dichalcogenoether ligands – synthesis, structures and reaction chemistry
The complexes [BX3(μ-L−L)BX3] (X = Cl, Br, I; L−L = EtS(CH2)2SEt, MeSe(CH2)2SeMe), [BX′3{o-C6H4(SMe)2}] (X’ = Cl, I), [(BBr3)2{o-C6H4(SMe)2}], [(BBr3)2{o-C6H4(SeMe)2}] and [BI3{o-C6H4(SeMe)2}] have been prepared as moisture-sensitive pale solids by reaction of the appropriate BX3 with the dichalcogenoether in anhydrous n-hexane solution, and characterised by microanalysis, IR and multinuclear (1H, 11B, 77Se{1H}) NMR spectroscopy. In contrast, the [BF3(μ-L−L)BF3], [(BF3)2{o-C6H4(SMe)2}] and [(BF3)2{o-C6H4(SeMe)2}], made from BF3 and the neat ligands, are viscous oils which have a significant vapour pressure of BF3 at ambient temperatures. X-ray crystal structures are reported for [BX3{μ-EtS(CH2)2SEt}BX3] (X = Cl, Br, I), [BBr3{μ-MeSe(CH2)2SeMe}BBr3], [BCl3{o-C6H4(SMe)2}] and [(BBr3)2{μ-o-C6H4(SeMe)2}]. The complexes [(BX3)2{MeTe(CH2)3TeMe}] (X = F, Cl, Br) have been identified in solution by multinuclear NMR spectroscopy, but decompose rapidly, whilst o-C6H4(TeMe)2 decomposes immediately on contact with BBr3 or BCl3. Dealkylation of some of the chalcogenoether ligands at room temperature by BI3, to yield complexes including [BI2{o-C6H4S(SMe)] and [BI2{o-C6H4Se(SeMe)], has been identified and the X-ray structure of [BI2{o-C6H4Se(SeMe)] determined. The trends in behaviour along the series of boron halides and with the various chalcogenoethers are described and compared with the behaviour of BX3 with neutral phosphorus and arsenic donor ligands (Burt et al., Inorg. Chem., 2016, 55, 8852) and with [BX3(EMe2)] (E = S, Se, Te) (Okio et al., J. Organometal. Chem., 2017, 848, 232).
Boron halides, Bidentate chalcogenoethers, selenoether, telluroether, thioether, Boron-11 NMR
0022-328X
140-149
Okio, Coco K.Y.A.
a079519f-6872-46d3-8bfe-f6c5f00557d0
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Monzittu, Francesco, Matteo
c0124f10-1f2e-47e5-85f4-138fab36b5d4
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Okio, Coco K.Y.A.
a079519f-6872-46d3-8bfe-f6c5f00557d0
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Monzittu, Francesco, Matteo
c0124f10-1f2e-47e5-85f4-138fab36b5d4
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Okio, Coco K.Y.A., Levason, William, Monzittu, Francesco, Matteo and Reid, Gillian (2017) Systematics of boron halide complexes with dichalcogenoether ligands – synthesis, structures and reaction chemistry. Journal of Organometallic Chemistry, 854, 140-149. (doi:10.1016/j.jorganchem.2017.11.018). (In Press)

Record type: Article

Abstract

The complexes [BX3(μ-L−L)BX3] (X = Cl, Br, I; L−L = EtS(CH2)2SEt, MeSe(CH2)2SeMe), [BX′3{o-C6H4(SMe)2}] (X’ = Cl, I), [(BBr3)2{o-C6H4(SMe)2}], [(BBr3)2{o-C6H4(SeMe)2}] and [BI3{o-C6H4(SeMe)2}] have been prepared as moisture-sensitive pale solids by reaction of the appropriate BX3 with the dichalcogenoether in anhydrous n-hexane solution, and characterised by microanalysis, IR and multinuclear (1H, 11B, 77Se{1H}) NMR spectroscopy. In contrast, the [BF3(μ-L−L)BF3], [(BF3)2{o-C6H4(SMe)2}] and [(BF3)2{o-C6H4(SeMe)2}], made from BF3 and the neat ligands, are viscous oils which have a significant vapour pressure of BF3 at ambient temperatures. X-ray crystal structures are reported for [BX3{μ-EtS(CH2)2SEt}BX3] (X = Cl, Br, I), [BBr3{μ-MeSe(CH2)2SeMe}BBr3], [BCl3{o-C6H4(SMe)2}] and [(BBr3)2{μ-o-C6H4(SeMe)2}]. The complexes [(BX3)2{MeTe(CH2)3TeMe}] (X = F, Cl, Br) have been identified in solution by multinuclear NMR spectroscopy, but decompose rapidly, whilst o-C6H4(TeMe)2 decomposes immediately on contact with BBr3 or BCl3. Dealkylation of some of the chalcogenoether ligands at room temperature by BI3, to yield complexes including [BI2{o-C6H4S(SMe)] and [BI2{o-C6H4Se(SeMe)], has been identified and the X-ray structure of [BI2{o-C6H4Se(SeMe)] determined. The trends in behaviour along the series of boron halides and with the various chalcogenoethers are described and compared with the behaviour of BX3 with neutral phosphorus and arsenic donor ligands (Burt et al., Inorg. Chem., 2016, 55, 8852) and with [BX3(EMe2)] (E = S, Se, Te) (Okio et al., J. Organometal. Chem., 2017, 848, 232).

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Accepted/In Press date: 21 November 2017
Keywords: Boron halides, Bidentate chalcogenoethers, selenoether, telluroether, thioether, Boron-11 NMR

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Local EPrints ID: 416655
URI: http://eprints.soton.ac.uk/id/eprint/416655
ISSN: 0022-328X
PURE UUID: 32110407-a2cd-41c2-bdd3-f9f2e73d352d
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Francesco, Matteo Monzittu: ORCID iD orcid.org/0000-0002-7080-3795
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 04 Jan 2018 17:30
Last modified: 07 Oct 2020 01:36

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Contributors

Author: Coco K.Y.A. Okio
Author: William Levason ORCID iD
Author: Francesco, Matteo Monzittu ORCID iD
Author: Gillian Reid ORCID iD

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