Kucera Benjamin E, Young Victor G, Brennessel William W, Ellis John E
Department of Chemistry, 207 Pleasant Street SE, University of Minnesota, Minneapolis, MN 55455, USA.
Department of Chemistry, 120 Trustee Road, University of Rochester, Rochester, NY 14627, USA.
Acta Crystallogr C Struct Chem. 2022 Mar 1;78(Pt 3):148-163. doi: 10.1107/S2053229622001255. Epub 2022 Feb 9.
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(μ-η:η:η-naphthalene)tetrakis(tetrahydrofuran)dipotassiumvanadium], [KV(CHO)(CH)] or [K(THF)][V(CH)] (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(η-naphthalene)vanadium tetrahydrofuran monosolvate, [K(CHNO)][V(CH)(CHP)]·CHO or [K([2.2.2]cryptand)][V(CH)(dmpe)]·THF [dmpe is 1,2-bis(dimethylphosphanyl)ethane] (4b). Notably, [V(CH)] 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 (PMe). 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 [(η-anthracene)(tetrahydrofuran)vanadium]-μ-η:η-anthracene-[(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium]-μ-η:η-anthracene-[(η-anthracene)(tetrahydrofuran)vanadium] tetrahydrofuran disolvate, [K(CHO)(CHO)][KV(CHO)(CHO)(CH)]·2CHO or [K(18-crown-6)][K(18-crown-6)(THF)][V(CH)(THF)]·2(THF) (5), which readily reacted with PMe and dmpe to give new vanadate salts. These were structurally characterized as (1,4,7,10,13,16-hexaoxacyclooctadecane)bis(tetrahydrofuran)potassium bis(η-anthracene)(trimethylphosphane)vanadium tetrahydrofuran monosolvate, [K(CHO)(CHO)][V(CH)(CHP)]·CHO or [K(18-crown-6)(THF)][V(CH)(PMe)]·THF (6), and tetrakis(1,2-dimethoxyethane)potassium bis(η-anthracene)[1,2-bis(dimethylphosphanyl)ethane]vanadium, [K(CHO)][V(CH)(CHP)] or [K(DME)][V(CH)(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, (μ-η:η:η-anthracene)(μ-η:η-anthracene)tris(tetrahydrofuran)sodiumdivanadium, [NaV(CH)(CHO)] or [Na(THF)][V(CH)] (8), containing the first reported dimetallabis(anthracene) sandwich compound.
在四氢呋喃（THF）中，萘钾（KNp）还原双（萘）钒（0）可得到一种高活性、热不稳定且至今无法分离的棕色物质，该物质可生成首例报道的双（萘）钒酸盐衍生物。从这些溶液中，已获得热稳定（298 K）且经结构表征的化合物，包括链状聚[双（μ-η:η:η-萘）四（四氢呋喃）二钾钒]的暗红色棒状晶体，[KV(CHO)(CH)]或[K(THF)][V(CH)]（3），以及（4,7,13,16,21,24-六氧杂-1,10-二氮杂双环[8.8.8]二十六烷）钾[1,2-双（二甲基膦基）乙烷]双（η-萘）钒四氢呋喃单溶剂合物的红色片状晶体，[K(CHNO)][V(CH)(CHP)]·CHO或[K([2.2.2]穴醚)][V(CH)(dmpe)]·THF [dmpe为1,2-双（二甲基膦基）乙烷]（4b）。值得注意的是，[V(CH)]是经结构验证的同配双（芳烃）金属酸根二价阴离子的唯一实例，它是在四氢呋喃中，于三甲基膦（PMe）存在下，通过萘钾进一步还原棕色物质而得到的。在四氢呋喃中向棕色物质中加入蒽（An），得到深紫色顺磁性晶体（1,4,7,10,13,16-六氧杂环十八烷）双（四氢呋喃）钾[(η-蒽）（四氢呋喃）钒]-μ-η:η-蒽-[(1,4,7,10,13,16-六氧杂环十八烷）钾]-μ-η:η-蒽-[(η-蒽）（四氢呋喃）钒]四氢呋喃二溶剂合物，[K(CHO)(CHO)][KV(CHO)(CHO)(CH)]·2CHO或[K(18-冠-6)][K(18-冠-6)(THF)][V(CH)(THF)]·2(THF)（5），它能与PMe和dmpe迅速反应生成新钒酸盐。这些新钒酸盐经结构表征为（1,4,7,10,13,16-六氧杂环十八烷）双（四氢呋喃）钾双（η-蒽）（三甲基膦）钒四氢呋喃单溶剂合物，[K(CHO)(CHO)][V(CH)(CHP)]·CHO或[K(18-冠-6)(THF)][V(CH)(PMe)]·THF（6），以及四（1,2-二甲氧基乙烷）钾双（η-蒽）[1,2-双（二甲基膦基）乙烷]钒，[K(CHO)][V(CH)(CHP)]或[K(DME)][V(CH)(dmpe)]（DME为1,2-二甲氧基乙烷）（7b）。最后三种结构包含首例已知的双（蒽）钒酸盐，因此是未知双（蒽）钒（0）的衍生物。尝试在四氢呋喃中制备5的钠盐类似物，结果却形成了一种独特的物质，（μ-η:η:η-蒽）（μ-η:η-蒽）三（四氢呋喃）钠二钒，[NaV(CH)(CHO)]或[Na(THF)][V(CH)]（8），它包含首例报道的双金属双（蒽）夹心化合物。
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