Scandium complexes with the tetraphenylethylene and anthracene dianions

John E. Ellis; Mikhail E. Minyaev; Ilya E. Nifant’Ev; Andrei V. Churakov

doi:10.1107/S2053229618007295

Scandium complexes with the tetraphenylethylene and anthracene dianions

John E. Ellis, Mikhail E. Minyaev, Ilya E. Nifant’Ev, Andrei V. Churakov

Chemistry (Twin Cities)

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

9 Scopus citations

Abstract

The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare-earth metal-carbon bonding. The crystal structures of (18-crown-6)bis(tetrahydrofuran-κO)sodium bis(η⁶-1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C₄H₈O)₂(C₁₂H₂₄O₆)][Sc(C₂₆H₂0)₂]·2C₄H₈O or [Na(18-crown-6)(THF)2][Sc(η⁶-C₂Ph₄)₂]·2(THF), (1b), (η⁵-1,3-diphenylcyclopentadienyl)(tetrahydrofuran-κO)(η⁶-1,1,2,2-tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C₁₇H₁₃)(C₂₆H₂₀)(C₄H₈O)]·0.5C₇H₈ or [(η⁵-1,3-Ph2C5H3)Sc(η6-C₂Ph₄)(THF)]·0.5(toluene), (5b), poly[[(μ²-η³:η³-anthracenediyl)bis(η6-anthracenediyl)bis(η⁵-1,3-diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K₂Sc₂(C₁₄H₁₀)₃(C₁₇H₁₃)₂(C₄H₈O)₄]·C₄H₈O}n or [K(THF)₂]₂[(1,3-Ph₂C₅H₃)₂Sc₂(C₁₄H₁₀)3]·THF, (6), and 1,4-diphenylcyclopenta-1,3-diene, C₁₇H₁₄, (3a), have been established. The [Sc(η⁶-C₂Ph₄)₂]-complex anion in (1b) contains the tetraphenylethylene dianion in a symmetrical bis-η3-allyl coordination mode. The complex homoleptic [Sc(η⁶-C₂Ph₄)₂]-anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The¹D¹H and¹³C{¹H}, and 2D COSY¹H-¹H and¹³C-¹H NMR data are presented for M[Sc(Ph₄C₂)₂]·xTHF [M = Na and x = 4 for (1a); M = K and x = 3.5 for (2a)] in THF-d8 media. Complex (5b) exhibits an unsymmetrical bis-η3-allyl coordination mode of the dianion, but this changes to a η4 coordination mode for (1,3-Ph₂C₅H₃)Sc(Ph₄C₂)(THF)2, (5a), in THF-d8 solution. A 45Sc NMR study of (2a) and UV-Vis studies of (1a), (2a) and (5a) indicate a significant covalent contribution to the Sc-Ph₄C₂ bond character. The unique Sc ate complex, (6), contains three anthracenide dianions demonstrating both a η6-coordination mode for two bent ligands and a μ²-η³:η³-bridging mode of a flat ligand. Each [(1,3-Ph₂C₅H₃)2Sc₂(C₁₄H₁₀)3]^2-dianionic unit is connected to four neighbouring units via short contacts with [K(THF)₂]⁺ cations, forming a two-dimensional coordination polymer framework parallel to (001).

Original language	English (US)
Pages (from-to)	769-781
Number of pages	13
Journal	Acta Crystallographica Section C: Structural Chemistry
Volume	74
DOIs	https://doi.org/10.1107/S2053229618007295
State	Published - 2018

Bibliographical note

Funding Information:
Funding for this research was provided by: US National Science Foundation program (grant No. CHE-0841014); The State Program of TIPS RAS supported by FASO Russia.

Publisher Copyright:
© 2018 International Union of Crystallography.

Keywords

Anthracene
Crystal structure
Dianion
Diphenylcyclopentadiene
NMR
Rare-earth complex
Scandium
Tetraphenylethylene

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@article{8fdee748121e4197af178a65a40bccad,

title = "Scandium complexes with the tetraphenylethylene and anthracene dianions",

abstract = "The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare-earth metal-carbon bonding. The crystal structures of (18-crown-6)bis(tetrahydrofuran-κO)sodium bis(η6-1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C4H8O)2(C12H24O6)][Sc(C26H20)2]·2C4H8O or [Na(18-crown-6)(THF)2][Sc(η6-C2Ph4)2]·2(THF), (1b), (η5-1,3-diphenylcyclopentadienyl)(tetrahydrofuran-κO)(η6-1,1,2,2-tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C17H13)(C26H20)(C4H8O)]·0.5C7H8 or [(η5-1,3-Ph2C5H3)Sc(η6-C2Ph4)(THF)]·0.5(toluene), (5b), poly[[(μ2-η3:η3-anthracenediyl)bis(η6-anthracenediyl)bis(η5-1,3-diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K2Sc2(C14H10)3(C17H13)2(C4H8O)4]·C4H8O}n or [K(THF)2]2[(1,3-Ph2C5H3)2Sc2(C14H10)3]·THF, (6), and 1,4-diphenylcyclopenta-1,3-diene, C17H14, (3a), have been established. The [Sc(η6-C2Ph4)2]-complex anion in (1b) contains the tetraphenylethylene dianion in a symmetrical bis-η3-allyl coordination mode. The complex homoleptic [Sc(η6-C2Ph4)2]-anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The1D1H and13C{1H}, and 2D COSY1H-1H and13C-1H NMR data are presented for M[Sc(Ph4C2)2]·xTHF [M = Na and x = 4 for (1a); M = K and x = 3.5 for (2a)] in THF-d8 media. Complex (5b) exhibits an unsymmetrical bis-η3-allyl coordination mode of the dianion, but this changes to a η4 coordination mode for (1,3-Ph2C5H3)Sc(Ph4C2)(THF)2, (5a), in THF-d8 solution. A 45Sc NMR study of (2a) and UV-Vis studies of (1a), (2a) and (5a) indicate a significant covalent contribution to the Sc-Ph4C2 bond character. The unique Sc ate complex, (6), contains three anthracenide dianions demonstrating both a η6-coordination mode for two bent ligands and a μ2-η3:η3-bridging mode of a flat ligand. Each [(1,3-Ph2C5H3)2Sc2(C14H10)3]2-dianionic unit is connected to four neighbouring units via short contacts with [K(THF)2]+ cations, forming a two-dimensional coordination polymer framework parallel to (001).",

keywords = "Anthracene, Crystal structure, Dianion, Diphenylcyclopentadiene, NMR, Rare-earth complex, Scandium, Tetraphenylethylene",

author = "Ellis, {John E.} and Minyaev, {Mikhail E.} and Nifant{\textquoteright}Ev, {Ilya E.} and Churakov, {Andrei V.}",

note = "Funding Information: Funding for this research was provided by: US National Science Foundation program (grant No. CHE-0841014); The State Program of TIPS RAS supported by FASO Russia. Publisher Copyright: {\textcopyright} 2018 International Union of Crystallography.",

year = "2018",

doi = "10.1107/S2053229618007295",

language = "English (US)",

volume = "74",

pages = "769--781",

journal = "Acta Crystallographica Section C: Structural Chemistry",

issn = "2053-2296",

publisher = "John Wiley and Sons Inc.",

}

TY - JOUR

T1 - Scandium complexes with the tetraphenylethylene and anthracene dianions

AU - Ellis, John E.

AU - Minyaev, Mikhail E.

AU - Nifant’Ev, Ilya E.

AU - Churakov, Andrei V.

N1 - Funding Information: Funding for this research was provided by: US National Science Foundation program (grant No. CHE-0841014); The State Program of TIPS RAS supported by FASO Russia. Publisher Copyright: © 2018 International Union of Crystallography.

PY - 2018

Y1 - 2018

N2 - The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare-earth metal-carbon bonding. The crystal structures of (18-crown-6)bis(tetrahydrofuran-κO)sodium bis(η6-1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C4H8O)2(C12H24O6)][Sc(C26H20)2]·2C4H8O or [Na(18-crown-6)(THF)2][Sc(η6-C2Ph4)2]·2(THF), (1b), (η5-1,3-diphenylcyclopentadienyl)(tetrahydrofuran-κO)(η6-1,1,2,2-tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C17H13)(C26H20)(C4H8O)]·0.5C7H8 or [(η5-1,3-Ph2C5H3)Sc(η6-C2Ph4)(THF)]·0.5(toluene), (5b), poly[[(μ2-η3:η3-anthracenediyl)bis(η6-anthracenediyl)bis(η5-1,3-diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K2Sc2(C14H10)3(C17H13)2(C4H8O)4]·C4H8O}n or [K(THF)2]2[(1,3-Ph2C5H3)2Sc2(C14H10)3]·THF, (6), and 1,4-diphenylcyclopenta-1,3-diene, C17H14, (3a), have been established. The [Sc(η6-C2Ph4)2]-complex anion in (1b) contains the tetraphenylethylene dianion in a symmetrical bis-η3-allyl coordination mode. The complex homoleptic [Sc(η6-C2Ph4)2]-anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The1D1H and13C{1H}, and 2D COSY1H-1H and13C-1H NMR data are presented for M[Sc(Ph4C2)2]·xTHF [M = Na and x = 4 for (1a); M = K and x = 3.5 for (2a)] in THF-d8 media. Complex (5b) exhibits an unsymmetrical bis-η3-allyl coordination mode of the dianion, but this changes to a η4 coordination mode for (1,3-Ph2C5H3)Sc(Ph4C2)(THF)2, (5a), in THF-d8 solution. A 45Sc NMR study of (2a) and UV-Vis studies of (1a), (2a) and (5a) indicate a significant covalent contribution to the Sc-Ph4C2 bond character. The unique Sc ate complex, (6), contains three anthracenide dianions demonstrating both a η6-coordination mode for two bent ligands and a μ2-η3:η3-bridging mode of a flat ligand. Each [(1,3-Ph2C5H3)2Sc2(C14H10)3]2-dianionic unit is connected to four neighbouring units via short contacts with [K(THF)2]+ cations, forming a two-dimensional coordination polymer framework parallel to (001).

AB - The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare-earth metal-carbon bonding. The crystal structures of (18-crown-6)bis(tetrahydrofuran-κO)sodium bis(η6-1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C4H8O)2(C12H24O6)][Sc(C26H20)2]·2C4H8O or [Na(18-crown-6)(THF)2][Sc(η6-C2Ph4)2]·2(THF), (1b), (η5-1,3-diphenylcyclopentadienyl)(tetrahydrofuran-κO)(η6-1,1,2,2-tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C17H13)(C26H20)(C4H8O)]·0.5C7H8 or [(η5-1,3-Ph2C5H3)Sc(η6-C2Ph4)(THF)]·0.5(toluene), (5b), poly[[(μ2-η3:η3-anthracenediyl)bis(η6-anthracenediyl)bis(η5-1,3-diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K2Sc2(C14H10)3(C17H13)2(C4H8O)4]·C4H8O}n or [K(THF)2]2[(1,3-Ph2C5H3)2Sc2(C14H10)3]·THF, (6), and 1,4-diphenylcyclopenta-1,3-diene, C17H14, (3a), have been established. The [Sc(η6-C2Ph4)2]-complex anion in (1b) contains the tetraphenylethylene dianion in a symmetrical bis-η3-allyl coordination mode. The complex homoleptic [Sc(η6-C2Ph4)2]-anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The1D1H and13C{1H}, and 2D COSY1H-1H and13C-1H NMR data are presented for M[Sc(Ph4C2)2]·xTHF [M = Na and x = 4 for (1a); M = K and x = 3.5 for (2a)] in THF-d8 media. Complex (5b) exhibits an unsymmetrical bis-η3-allyl coordination mode of the dianion, but this changes to a η4 coordination mode for (1,3-Ph2C5H3)Sc(Ph4C2)(THF)2, (5a), in THF-d8 solution. A 45Sc NMR study of (2a) and UV-Vis studies of (1a), (2a) and (5a) indicate a significant covalent contribution to the Sc-Ph4C2 bond character. The unique Sc ate complex, (6), contains three anthracenide dianions demonstrating both a η6-coordination mode for two bent ligands and a μ2-η3:η3-bridging mode of a flat ligand. Each [(1,3-Ph2C5H3)2Sc2(C14H10)3]2-dianionic unit is connected to four neighbouring units via short contacts with [K(THF)2]+ cations, forming a two-dimensional coordination polymer framework parallel to (001).

KW - Anthracene

KW - Crystal structure

KW - Dianion

KW - Diphenylcyclopentadiene

KW - NMR

KW - Rare-earth complex

KW - Scandium

KW - Tetraphenylethylene

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UR - http://www.scopus.com/inward/citedby.url?scp=85048258194&partnerID=8YFLogxK

U2 - 10.1107/S2053229618007295

DO - 10.1107/S2053229618007295

M3 - Article

C2 - 29870014

AN - SCOPUS:85048258194

SN - 2053-2296

VL - 74

SP - 769

EP - 781

JO - Acta Crystallographica Section C: Structural Chemistry

JF - Acta Crystallographica Section C: Structural Chemistry

ER -

Scandium complexes with the tetraphenylethylene and anthracene dianions

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