Syntheses and crystal structures of new naphthalene- and anthracene-vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran)3][V2(anthracene)2]

Benjamin E. Kucera; Victor G. Young; William W. Brennessel; John E Ellis

doi:10.1107/S2053229622001255

Syntheses and crystal structures of new naphthalene- and anthracene-vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran)₃][V₂(anthracene)₂]

Benjamin E. Kucera, Victor G. Young, William W. Brennessel, John E Ellis

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

3 Scopus citations

Abstract

Reduction of bis(naphthalene)vanadium(0) by potassium naphthalene (KNp) in tetrahydrofuran (THF) provides a highly reactive, thermolabile, and so far unisolable brown substance, which affords the first reported derivatives of bis(naphthalene)vanadates. From these solutions, thermally stable (298 K) and structurally characterized compounds have been obtained, including dark-red rods of catena-poly[bis(μ₃-η⁴:η⁶:η⁴-naphthalene)tetrakis(tetrahydrofuran)dipotassiumvanadium], [K₂V(C₄H₈O)₄(C₁₀H₈)₂]_n or [K(THF)₂]₂[V(C₁₀H₈)₂] (3), and red plates of (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)potassium [1,2-bis(dimethylphosphanyl)ethane]bis(η⁴-naphthalene)vanadium tetrahydrofuran monosolvate, [K(C₁₈H₃₆N₂O₆)][V(C₁₀H₈)₂(C₆H₁₆P₂)].C₄H₈O or [K([2.2.2]cryptand)][V(C₁₀H₈)₂(dmpe)].THF [dmpe is 1,2-bis(dimethylphosphanyl)-ethane] (4b). Notably, [V(C₁₀H₈)₂]^2- is the only example of a structurally authenticated homoleptic bis(arene)metallate dianion and was obtained by further reduction of the brown material by KNp in THF, in the presence of trimethylphosphane (PMe₃). Addition of anthracene (An) to the brown material in THF afforded deep-violet and paramagnetic crystalline (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium [(η⁴-anthracene)(tetra-hydrofuran)vanadium]-μ-η⁴:η²-anthracene-[(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium]-μ-η²:η⁴-anthracene-[(η⁴-anthracene)(tetrahydrofuran)vanadium] tetrahydrofuran disolvate, [K(C₁₂H₂₄O₆)(C₄H₈O)₂][KV₂(C₁₂H₂₄O₆)(C₄H₈O)₂(C₁₄H₁₀)₄].2C₄H₈O or [K(18-crown-6)][K(18-crown-6)(THF)₂][V(C₁₄H₁₀)₂(THF)]_2.2(THF) (5), which readily reacted with PMe₃ and dmpe to give new vanadate salts. These were structurally characterized as (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium bis(η⁴-anthracene)(trimethylphosphane)vanadium tetrahydrofuran monosolvate, [K(C₁₂H₂₄O₆)(C₄H₈O)₂][V(C₁₄H₁₀)₂(C₃H₉P)].C₄H₈O or [K(18-crown-6)(THF)₂][V(C₁₄H₁₀)₂(PMe₃)].THF (6), and tetrakis(1,2-dimethoxyethane)potassium bis(η⁴-anthracene)[1,2-bis(dimethylphosphanyl)ethane]vanadium, [K(C₄H₁₀O₂)₄][V(C₁₄H₁₀)₂(C₆H₁₆P₂)] or [K(DME)₄][V(C₁₄H₁₀)₂(dmpe)] (DME is 1,2-dimethoxyethane) (7b). The last three structures contain the first known bis(anthracene)vanadates and are thereby derivatives of the unknown bis(anthracene)vanadium(0). Attempts to obtain the sodium salt analog of 5 in THF resulted instead in the formation of a unique substance, (μ₃-η⁶:η⁶:η⁶-anthracene)(μ₂-η⁶:η⁶-anthracene)-tris(tetrahydrofuran)sodiumdivanadium, [NaV₂(C₁₄H₁₀)₂(C₄H₈O)₃] or [Na(THF)₃][V₂(C₁₄H₁₀)₂] (8), containing the first reported dimetallabis(anthracene) sandwich compound.

Original language	English (US)
Pages (from-to)	148-163
Number of pages	16
Journal	Acta Crystallographica Section C: Structural Chemistry
Volume	78
DOIs	https://doi.org/10.1107/S2053229622001255
State	Published - Mar 1 2022
Externally published	Yes

Bibliographical note

Funding Information:
Funding for this research was provided by the US National Science Foundation, donors of the Petroleum Research Foundation, administered by the American Chemical Society, and Research Gift Support, administered by the University of Minnesota Foundation. JEE thanks David Blank, Connie Lu, Kent Mann, Larry Que Jr, Ian Tonks, and Chuck Tomlinson for support, assistance, and inspiration during his transition to Emeritus status in the Department of Chemistry, University of Minnesota.

Publisher Copyright:
© 2022 International Union of Crystallography. All rights reserved.

Keywords

anthracene
bis(polyarene)vanadates
crystal structure
dimetallabis(anthracene) sandwich complex
naphthalene

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Syntheses and crystal structures of new naphthalene- and anthracene-vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran)₃][V₂(anthracene)₂]. / Kucera, Benjamin E.; Young, Victor G.; Brennessel, William W. et al.
In: Acta Crystallographica Section C: Structural Chemistry, Vol. 78, 01.03.2022, p. 148-163.

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

@article{a6031fa1ecef4a2ca352455a7b19a9eb,

title = "Syntheses and crystal structures of new naphthalene- and anthracene-vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex: [Na(tetrahydrofuran)3][V2(anthracene)2]",

abstract = "Reduction of bis(naphthalene)vanadium(0) by potassium naphthalene (KNp) in tetrahydrofuran (THF) provides a highly reactive, thermolabile, and so far unisolable brown substance, which affords the first reported derivatives of bis(naphthalene)vanadates. From these solutions, thermally stable (298 K) and structurally characterized compounds have been obtained, including dark-red rods of catena-poly[bis(μ3-η4:η6:η4-naphthalene)tetrakis(tetrahydrofuran)dipotassiumvanadium], [K2V(C4H8O)4(C10H8)2]n or [K(THF)2]2[V(C10H8)2] (3), and red plates of (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)potassium [1,2-bis(dimethylphosphanyl)ethane]bis(η4-naphthalene)vanadium tetrahydrofuran monosolvate, [K(C18H36N2O6)][V(C10H8)2(C6H16P2)].C4H8O or [K([2.2.2]cryptand)][V(C10H8)2(dmpe)].THF [dmpe is 1,2-bis(dimethylphosphanyl)-ethane] (4b). Notably, [V(C10H8)2]2- is the only example of a structurally authenticated homoleptic bis(arene)metallate dianion and was obtained by further reduction of the brown material by KNp in THF, in the presence of trimethylphosphane (PMe3). Addition of anthracene (An) to the brown material in THF afforded deep-violet and paramagnetic crystalline (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium [(η4-anthracene)(tetra-hydrofuran)vanadium]-μ-η4:η2-anthracene-[(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium]-μ-η2:η4-anthracene-[(η4-anthracene)(tetrahydrofuran)vanadium] tetrahydrofuran disolvate, [K(C12H24O6)(C4H8O)2][KV2(C12H24O6)(C4H8O)2(C14H10)4].2C4H8O or [K(18-crown-6)][K(18-crown-6)(THF)2][V(C14H10)2(THF)]2.2(THF) (5), which readily reacted with PMe3 and dmpe to give new vanadate salts. These were structurally characterized as (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium bis(η4-anthracene)(trimethylphosphane)vanadium tetrahydrofuran monosolvate, [K(C12H24O6)(C4H8O)2][V(C14H10)2(C3H9P)].C4H8O or [K(18-crown-6)(THF)2][V(C14H10)2(PMe3)].THF (6), and tetrakis(1,2-dimethoxyethane)potassium bis(η4-anthracene)[1,2-bis(dimethylphosphanyl)ethane]vanadium, [K(C4H10O2)4][V(C14H10)2(C6H16P2)] or [K(DME)4][V(C14H10)2(dmpe)] (DME is 1,2-dimethoxyethane) (7b). The last three structures contain the first known bis(anthracene)vanadates and are thereby derivatives of the unknown bis(anthracene)vanadium(0). Attempts to obtain the sodium salt analog of 5 in THF resulted instead in the formation of a unique substance, (μ3-η6:η6:η6-anthracene)(μ2-η6:η6-anthracene)-tris(tetrahydrofuran)sodiumdivanadium, [NaV2(C14H10)2(C4H8O)3] or [Na(THF)3][V2(C14H10)2] (8), containing the first reported dimetallabis(anthracene) sandwich compound.",

keywords = "anthracene, bis(polyarene)vanadates, crystal structure, dimetallabis(anthracene) sandwich complex, naphthalene",

author = "Kucera, {Benjamin E.} and Young, {Victor G.} and Brennessel, {William W.} and Ellis, {John E}",

note = "Funding Information: Funding for this research was provided by the US National Science Foundation, donors of the Petroleum Research Foundation, administered by the American Chemical Society, and Research Gift Support, administered by the University of Minnesota Foundation. JEE thanks David Blank, Connie Lu, Kent Mann, Larry Que Jr, Ian Tonks, and Chuck Tomlinson for support, assistance, and inspiration during his transition to Emeritus status in the Department of Chemistry, University of Minnesota. Publisher Copyright: {\textcopyright} 2022 International Union of Crystallography. All rights reserved.",

year = "2022",

month = mar,

day = "1",

doi = "10.1107/S2053229622001255",

language = "English (US)",

volume = "78",

pages = "148--163",

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

issn = "2053-2296",

publisher = "John Wiley and Sons Inc.",

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TY - JOUR

T1 - Syntheses and crystal structures of new naphthalene- and anthracene-vanadate salts and an unprecedented dimetallabis(anthracene) sandwich complex

T2 - [Na(tetrahydrofuran)3][V2(anthracene)2]

AU - Kucera, Benjamin E.

AU - Young, Victor G.

AU - Brennessel, William W.

AU - Ellis, John E

N1 - Funding Information: Funding for this research was provided by the US National Science Foundation, donors of the Petroleum Research Foundation, administered by the American Chemical Society, and Research Gift Support, administered by the University of Minnesota Foundation. JEE thanks David Blank, Connie Lu, Kent Mann, Larry Que Jr, Ian Tonks, and Chuck Tomlinson for support, assistance, and inspiration during his transition to Emeritus status in the Department of Chemistry, University of Minnesota. Publisher Copyright: © 2022 International Union of Crystallography. All rights reserved.

PY - 2022/3/1

Y1 - 2022/3/1

N2 - Reduction of bis(naphthalene)vanadium(0) by potassium naphthalene (KNp) in tetrahydrofuran (THF) provides a highly reactive, thermolabile, and so far unisolable brown substance, which affords the first reported derivatives of bis(naphthalene)vanadates. From these solutions, thermally stable (298 K) and structurally characterized compounds have been obtained, including dark-red rods of catena-poly[bis(μ3-η4:η6:η4-naphthalene)tetrakis(tetrahydrofuran)dipotassiumvanadium], [K2V(C4H8O)4(C10H8)2]n or [K(THF)2]2[V(C10H8)2] (3), and red plates of (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)potassium [1,2-bis(dimethylphosphanyl)ethane]bis(η4-naphthalene)vanadium tetrahydrofuran monosolvate, [K(C18H36N2O6)][V(C10H8)2(C6H16P2)].C4H8O or [K([2.2.2]cryptand)][V(C10H8)2(dmpe)].THF [dmpe is 1,2-bis(dimethylphosphanyl)-ethane] (4b). Notably, [V(C10H8)2]2- is the only example of a structurally authenticated homoleptic bis(arene)metallate dianion and was obtained by further reduction of the brown material by KNp in THF, in the presence of trimethylphosphane (PMe3). Addition of anthracene (An) to the brown material in THF afforded deep-violet and paramagnetic crystalline (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium [(η4-anthracene)(tetra-hydrofuran)vanadium]-μ-η4:η2-anthracene-[(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium]-μ-η2:η4-anthracene-[(η4-anthracene)(tetrahydrofuran)vanadium] tetrahydrofuran disolvate, [K(C12H24O6)(C4H8O)2][KV2(C12H24O6)(C4H8O)2(C14H10)4].2C4H8O or [K(18-crown-6)][K(18-crown-6)(THF)2][V(C14H10)2(THF)]2.2(THF) (5), which readily reacted with PMe3 and dmpe to give new vanadate salts. These were structurally characterized as (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium bis(η4-anthracene)(trimethylphosphane)vanadium tetrahydrofuran monosolvate, [K(C12H24O6)(C4H8O)2][V(C14H10)2(C3H9P)].C4H8O or [K(18-crown-6)(THF)2][V(C14H10)2(PMe3)].THF (6), and tetrakis(1,2-dimethoxyethane)potassium bis(η4-anthracene)[1,2-bis(dimethylphosphanyl)ethane]vanadium, [K(C4H10O2)4][V(C14H10)2(C6H16P2)] or [K(DME)4][V(C14H10)2(dmpe)] (DME is 1,2-dimethoxyethane) (7b). The last three structures contain the first known bis(anthracene)vanadates and are thereby derivatives of the unknown bis(anthracene)vanadium(0). Attempts to obtain the sodium salt analog of 5 in THF resulted instead in the formation of a unique substance, (μ3-η6:η6:η6-anthracene)(μ2-η6:η6-anthracene)-tris(tetrahydrofuran)sodiumdivanadium, [NaV2(C14H10)2(C4H8O)3] or [Na(THF)3][V2(C14H10)2] (8), containing the first reported dimetallabis(anthracene) sandwich compound.

AB - Reduction of bis(naphthalene)vanadium(0) by potassium naphthalene (KNp) in tetrahydrofuran (THF) provides a highly reactive, thermolabile, and so far unisolable brown substance, which affords the first reported derivatives of bis(naphthalene)vanadates. From these solutions, thermally stable (298 K) and structurally characterized compounds have been obtained, including dark-red rods of catena-poly[bis(μ3-η4:η6:η4-naphthalene)tetrakis(tetrahydrofuran)dipotassiumvanadium], [K2V(C4H8O)4(C10H8)2]n or [K(THF)2]2[V(C10H8)2] (3), and red plates of (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane)potassium [1,2-bis(dimethylphosphanyl)ethane]bis(η4-naphthalene)vanadium tetrahydrofuran monosolvate, [K(C18H36N2O6)][V(C10H8)2(C6H16P2)].C4H8O or [K([2.2.2]cryptand)][V(C10H8)2(dmpe)].THF [dmpe is 1,2-bis(dimethylphosphanyl)-ethane] (4b). Notably, [V(C10H8)2]2- is the only example of a structurally authenticated homoleptic bis(arene)metallate dianion and was obtained by further reduction of the brown material by KNp in THF, in the presence of trimethylphosphane (PMe3). Addition of anthracene (An) to the brown material in THF afforded deep-violet and paramagnetic crystalline (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium [(η4-anthracene)(tetra-hydrofuran)vanadium]-μ-η4:η2-anthracene-[(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium]-μ-η2:η4-anthracene-[(η4-anthracene)(tetrahydrofuran)vanadium] tetrahydrofuran disolvate, [K(C12H24O6)(C4H8O)2][KV2(C12H24O6)(C4H8O)2(C14H10)4].2C4H8O or [K(18-crown-6)][K(18-crown-6)(THF)2][V(C14H10)2(THF)]2.2(THF) (5), which readily reacted with PMe3 and dmpe to give new vanadate salts. These were structurally characterized as (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium bis(η4-anthracene)(trimethylphosphane)vanadium tetrahydrofuran monosolvate, [K(C12H24O6)(C4H8O)2][V(C14H10)2(C3H9P)].C4H8O or [K(18-crown-6)(THF)2][V(C14H10)2(PMe3)].THF (6), and tetrakis(1,2-dimethoxyethane)potassium bis(η4-anthracene)[1,2-bis(dimethylphosphanyl)ethane]vanadium, [K(C4H10O2)4][V(C14H10)2(C6H16P2)] or [K(DME)4][V(C14H10)2(dmpe)] (DME is 1,2-dimethoxyethane) (7b). The last three structures contain the first known bis(anthracene)vanadates and are thereby derivatives of the unknown bis(anthracene)vanadium(0). Attempts to obtain the sodium salt analog of 5 in THF resulted instead in the formation of a unique substance, (μ3-η6:η6:η6-anthracene)(μ2-η6:η6-anthracene)-tris(tetrahydrofuran)sodiumdivanadium, [NaV2(C14H10)2(C4H8O)3] or [Na(THF)3][V2(C14H10)2] (8), containing the first reported dimetallabis(anthracene) sandwich compound.

KW - anthracene

KW - bis(polyarene)vanadates

KW - crystal structure

KW - dimetallabis(anthracene) sandwich complex

KW - naphthalene

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