Structural and Synthetic Insights into Sodium‐Mediated‐Ferration of Fluoroarenes

نویسندگان

چکیده

Exploiting chemical cooperation between Na and Fe(II) within the bimetallic base [dioxane ⋅ NaFe(HMDS)3] (I), (dioxane=1,4-dioxane, HMDS=N(SiMe3)2) selective ferration of fluorobenzene, 1-fluoronaphthalene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 1-bromo-3,5-difluorobenzene, 3-fluoroanisole 3,5-difluoroanisole has been realized, affording sodium ferrates Na(HMDS)(2-F-C6H4)Fe(HMDS)]∞ (1), Na(HMDS)(2-F-C10H6)Fe(HMDS)]∞ (2), {Na(HMDS)(2,5-F2-C6H3)Fe(HMDS)}2]∞ (3), {Na(HMDS)(2,3,6-F3-C6H2)Fe(HMDS)}2]∞ (4), [(dioxane)1.5 Na(HMDS)(2,4,6-F3-C6H2)Fe(HMDS)]2 (5), {Na(HMDS)(4-Br-2,6-F2-C6H2)Fe(HMDS)2] (6), [{(dioxane)2 Na2Fe(HMDS)2(2-methoxy-6-F-C6H3)}+{Fe(HMDS)3}−]∞ (7) {Na(HMDS)(4-methoxy-2,6-F2-C6H2)Fe(HMDS)}2]∞ (8), respectively. Reactions take place under mild reaction conditions, with excellent control selectivity no competing C−F bond activation is observed. Showcasing complex polymeric arrangements in some cases, structures compounds 1–8 have determined by X-ray crystallographic studies. In all centers occupy position relevant fluoroarene that was previously filled a proton, confirming these metallations are actually processes whereas atoms prefer to form Na⋅⋅⋅F dative interactions. Compounds thermally stable do not undergo benzyne formation (through NaF elimination) their contrasts inertness Fe(HMDS)2 which fails act as metallate fluoroarenes.

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ژورنال

عنوان ژورنال: Helvetica Chimica Acta

سال: 2021

ISSN: ['1522-2675', '0018-019X']

DOI: https://doi.org/10.1002/hlca.202100206