Double-stranded cycles: toward C84's belt region.
The reactivity of the double-stranded hydrocarbon cycle with two ether bridges (1) toward iodotrimethylsilane (TMSI) was investigated in some detail. The carbon skeleton of cycle 1 resembles the belt region of a C84 fullerene which makes it a potential precursor to the long sought after fully aromatic derivative. Upon exposure to TMSI, cycle 1 undergoes a cascade of reactions which involve different states of iodination/reduction which ultimately lead to the hydrogenated cycle 5a, whose structure was proven by single-crystal X-ray analysis. A deeper insight into mechanistic aspects of this sequence of conversions was gained by performing the reaction under dry and wet conditions, whereby the latter involved both normal and deuterated water. With the help of detailed NMR correlation studies and DFT computations, all important aspects were clarified including an unexpected selective H/D exchange at the naphthalenic moieties.
Stuparu
Mihaiela
M
Institute of Polymers, Department of Materials, ETH-Zürich, Wolfgang Pauli Strasse 10, HCI J 541, CH-8093 Zürich, Switzerland.
Gramlich
Volker
V
Stanger
Amnon
A
Schlüter
A Dieter
AD
D018360:Crystallography, X-Ray; D037741:Fullerenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D012680:Sensitivity and Specificity; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
D037741:Fullerenes; D014297:Trimethylsilyl Compounds; C027752:iodotrimethylsilane