posted on 2014-12-22, 00:00authored byAlejandra Enrı́quez, Ana Ma. González-Vadillo, Ignacio Martı́nez-Montero, Sonia Bruña, Laura Leemans, Isabel Cuadrado
The
application of ethynylferrocene, FcCCH (1), as
a highly efficient electroactive precursor for the thiol–yne
click reaction is presented. For this purpose, a wide range of functionalized
thiols, namely 2-mercaptoethanol, 1-thioglycerol, 3-mercaptopropionic
acid, 4-aminothiophenol, and benzene-1,3-dithiol as well as tetrathiol
pentaerythritol tetrakis(3-mercaptopropionate), were investigated.
This facile thiol–ethynylferrocene radical reaction has resulted
in the quantitative formation and isolation of the newly ferrocenyl–vinyl
sulfides FcCHCHS(CH2)2OH (2Z and 2E), FcCHCHSCH2CH(OH)CH2OH (3Z and 3E), FcCHCHS(CH2)2COOH (4Z and 4E), FcC(CH2)S(1,4-C6H4)NH2 (5α), FcCHCHS(1,3-C6H4)SCHCHFc (6), and [FcCHCHS(CH2)2COOCH2]4C (7). Thiol–ethynylferrocene reactions have been initiated either
by heat, in toluene with AIBN, or by UV light irradiation in THF in
the presence of DMPA as photoinitiator. The outcome of the hydrothiolation
of ethynylferrocene strongly depends on the thiol structure and on
the initiation method employed. A simple mixing of metallocene 1 with the thiol HS(CH2)2OH or HS(CH2)2COOH in a proper ratio, in THF at 20 °C,
in a initiator-free thiol–yne reaction, causes hydrothiolation
of 1 to occur, allowing for the formation of vinyl sulfides 2Z, 2E and 4Z, 4E in good isolated
yields. In contrast to the bis-addition typically observed for thiol–yne
reactions, no double hydrothiolation to FcCCH has been observed
for any of the thiols under any conditions studied. Electrochemical
studies showed that tetrametallic compound 7, containing
four sulfur-bridged ferrocenyl–vinyl moieties, behaves as a
tetrapodal adsorbate molecule, exhibiting excellent chemisorption
properties, and spontaneously forms robustly adsorbed 7 films onto Au or Pt electrode surfaces.