TY - JOUR
T1 - Electrochemistry of ruthenium metallocenes
T2 - Part 3. Synthesis and properties of ruthenium [22]paracyclophane complexes with methacrylic acid and methacrylate ester substitutents
AU - Gollas, Bernhard
AU - Speiser, Bernd
AU - Zagos, Ioannis
AU - Maichle-Mössmer, Cäcilia
N1 - Funding Information:
The authors thank the Deutsche Forschungsgemeinschaft, Bonn-Bad Godesberg, Germany (Heisenberg fellowship for BS; SPP ‘Elektrochemische Grundlagen der Nanotechnologie’; Graduiertenkolleg ‘Chemie in Interphasen’) and the Fonds der Chemischen Industrie, Frankfurt/Main, Germany, for financial support. We are indepted to Degussa AG, Frankfurt/Main, for gifts of ruthenium trichloride and Pt wire, to V. Boekelheide, Eugene/OR, USA, for a gift of [2 2 ](1,4)cyclophane, and H. Hopf, Braunschweig, Germany, for providing us with details of the synthetic procedure leading to compounds 15 and 18 , as well as samples of 16 and 17 . B. Krauß is acknowledged for determining the mid-point potentials of 2 and 3 during work on his diploma thesis. We thank M.E. Maier, Tübingen, for the use of his FT-IR spectrometer.
PY - 2000/5/15
Y1 - 2000/5/15
N2 - Four [22](1,4)cyclophanes bearing one or two methacrylate ethyl ester and methacrylic acid substituents and ruthenium arene complexes of these compounds are synthesized. The structure of the ligands and the complexes is characterized by NMR spectroscopic techniques. For some of the ligands X-ray crystal structure analyses support the assignments. The mono-substituted [22](1,4)cyclophanes prefer to form anti-complexes, with the Ru central atom bound to the unsubstituted aromatic deck. The irreversible electrochemical oxidation of the cyclophanes is studied by cyclic voltammetry, and, in contrast to mono- and divinyl[22](1,4)cyclophanes does not produce permanent films on the electrode. The electrochemical reduction of the complexes proceeds as a two-electron process and produces the kinetically stable corresponding Ru0 species. The anodic oxidation of the title compounds is irreversible and leads to filming of the electrode surface.
AB - Four [22](1,4)cyclophanes bearing one or two methacrylate ethyl ester and methacrylic acid substituents and ruthenium arene complexes of these compounds are synthesized. The structure of the ligands and the complexes is characterized by NMR spectroscopic techniques. For some of the ligands X-ray crystal structure analyses support the assignments. The mono-substituted [22](1,4)cyclophanes prefer to form anti-complexes, with the Ru central atom bound to the unsubstituted aromatic deck. The irreversible electrochemical oxidation of the cyclophanes is studied by cyclic voltammetry, and, in contrast to mono- and divinyl[22](1,4)cyclophanes does not produce permanent films on the electrode. The electrochemical reduction of the complexes proceeds as a two-electron process and produces the kinetically stable corresponding Ru0 species. The anodic oxidation of the title compounds is irreversible and leads to filming of the electrode surface.
KW - Cyclic voltammetry
KW - Cyclophanes
KW - Electrode modification
KW - NMR spectroscopy
KW - Ruthenium complexes
UR - http://www.scopus.com/inward/record.url?scp=0004505204&partnerID=8YFLogxK
U2 - 10.1016/s0022-328x(00)00121-2
DO - 10.1016/s0022-328x(00)00121-2
M3 - Article
AN - SCOPUS:0004505204
SN - 0022-328X
VL - 602
SP - 75
EP - 90
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -