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)|
|Number of pages||16|
|Journal||Acta Crystallographica Section C: Structural Chemistry|
|Issue number||Pt 3|
|State||Published - Mar 1 2022|
Bibliographical noteFunding 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.
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- crystal structure
- dimetallabis(anthracene) sandwich complex
PubMed: MeSH publication types
- Journal Article