Carbon-Rich Trinuclear Octamethylferrocenophanes

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Abstract

Several trinuclear ferrocenes are obtained by Friedel-Crafts reaction of octamethylferrocene with ferrocenoyl chloride and subsequent modifications. 1,1'-Diferrocenoyloctamethylferrocene (3) is transformed to the divinyl deriv. (4a) by reaction with MeLi and AlCl3.  The reactive 4a cyclizes spontaneously to a [4]ferrocenophane with buta-1,3-diene handle (5) or in the presence of AlCl3 to a [3]ferrocenophane with propene handle (6).  Structure assignments are supported by X-ray crystallog. and NMR spectroscopy, and mechanisms are proposed.  Electrochem. behavior of the compds. was investigated with cyclic voltammetry, and assignments of the redox processes were carried out with the aid of d. functional theory calcns.  The synthesized compds. and demonstrated transformations represent useful tools for prepn. of materials for charge-transport studies in metal-mol.-metal junctions.
Original languageEnglish
Pages (from-to)3789–3799
JournalInorganic Chemistry
Volume56
Issue number6
DOIs
Publication statusPublished - 18 Mar 2019

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Carbon
Friedel-Craft reaction
Metals
Friedel-Crafts reaction
ferrocenes
carbon
dienes
metals
Nuclear magnetic resonance spectroscopy
Cyclic voltammetry
Charge transfer
Chlorides
chlorides
X rays
nuclear magnetic resonance
spectroscopy
x rays
aluminum chloride
propylene
1,3-butadiene

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title = "Carbon-Rich Trinuclear Octamethylferrocenophanes",
abstract = "Several trinuclear ferrocenes are obtained by Friedel-Crafts reaction of octamethylferrocene with ferrocenoyl chloride and subsequent modifications. 1,1'-Diferrocenoyloctamethylferrocene (3) is transformed to the divinyl deriv. (4a) by reaction with MeLi and AlCl3.  The reactive 4a cyclizes spontaneously to a [4]ferrocenophane with buta-1,3-diene handle (5) or in the presence of AlCl3 to a [3]ferrocenophane with propene handle (6).  Structure assignments are supported by X-ray crystallog. and NMR spectroscopy, and mechanisms are proposed.  Electrochem. behavior of the compds. was investigated with cyclic voltammetry, and assignments of the redox processes were carried out with the aid of d. functional theory calcns.  The synthesized compds. and demonstrated transformations represent useful tools for prepn. of materials for charge-transport studies in metal-mol.-metal junctions.",
author = "Max Roemer and Wild, {Duncan A.} and Sobolev, {Alexandre N.} and Skelton, {Brian W.} and Nealon, {Gareth L.} and Piggott, {Matthew J.} and Koutsantonis, {George A.}",
year = "2019",
month = "3",
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doi = "10.1021/acs.inorgchem.8b03389",
language = "English",
volume = "56",
pages = "3789–3799",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Carbon-Rich Trinuclear Octamethylferrocenophanes

AU - Roemer, Max

AU - Wild, Duncan A.

AU - Sobolev, Alexandre N.

AU - Skelton, Brian W.

AU - Nealon, Gareth L.

AU - Piggott, Matthew J.

AU - Koutsantonis, George A.

PY - 2019/3/18

Y1 - 2019/3/18

N2 - Several trinuclear ferrocenes are obtained by Friedel-Crafts reaction of octamethylferrocene with ferrocenoyl chloride and subsequent modifications. 1,1'-Diferrocenoyloctamethylferrocene (3) is transformed to the divinyl deriv. (4a) by reaction with MeLi and AlCl3.  The reactive 4a cyclizes spontaneously to a [4]ferrocenophane with buta-1,3-diene handle (5) or in the presence of AlCl3 to a [3]ferrocenophane with propene handle (6).  Structure assignments are supported by X-ray crystallog. and NMR spectroscopy, and mechanisms are proposed.  Electrochem. behavior of the compds. was investigated with cyclic voltammetry, and assignments of the redox processes were carried out with the aid of d. functional theory calcns.  The synthesized compds. and demonstrated transformations represent useful tools for prepn. of materials for charge-transport studies in metal-mol.-metal junctions.

AB - Several trinuclear ferrocenes are obtained by Friedel-Crafts reaction of octamethylferrocene with ferrocenoyl chloride and subsequent modifications. 1,1'-Diferrocenoyloctamethylferrocene (3) is transformed to the divinyl deriv. (4a) by reaction with MeLi and AlCl3.  The reactive 4a cyclizes spontaneously to a [4]ferrocenophane with buta-1,3-diene handle (5) or in the presence of AlCl3 to a [3]ferrocenophane with propene handle (6).  Structure assignments are supported by X-ray crystallog. and NMR spectroscopy, and mechanisms are proposed.  Electrochem. behavior of the compds. was investigated with cyclic voltammetry, and assignments of the redox processes were carried out with the aid of d. functional theory calcns.  The synthesized compds. and demonstrated transformations represent useful tools for prepn. of materials for charge-transport studies in metal-mol.-metal junctions.

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U2 - 10.1021/acs.inorgchem.8b03389

DO - 10.1021/acs.inorgchem.8b03389

M3 - Article

VL - 56

SP - 3789

EP - 3799

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 6

ER -