The reaction of decamethylsilicocene, (Me5C5)2Si, with the proton-transfer reagent Me5C5H2+B(C6F5)4- produces the salt (Me5C5)Si+ B(C6F5)4(2), which can be isolated as a colorless solid that is stable in the absence of air and moisture. The crystal structure reveals the presence of a cationic pi complex with an eta5-pentamethylcyclopentadienyl ligand bound to a bare silicon center. The 29Si nuclear magnetic resonance at very high field (delta = - 400.2 parts per million) is typical of a pi complex of divalent silicon. The (eta5-Me5C5)Si+ cation in 2 can be regarded as the "resting state" of a silyliumylidene-type (eta1-Me5C5)Si+ cation. The availability of 2 opens new synthetic avenues in organosilicon chemistry. For example, 2 reacted with lithium bis(trimethylsilyl)amide to give the disilene E-[(eta1-Me5C5)[N(SiMe3)2]Si]2(3).
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http://dx.doi.org/10.1126/science.1099879 | DOI Listing |
Chem Commun (Camb)
September 2006
Department of Chemistry, University of Bielefeld, Universitätsstrasse 25, D-33615 Bielefeld, Germany.
The pentamethylcyclopentadienylsilicon(II) cation, Me5C5Si+, opens up access to novel silicocene derivatives; the penta-iso-propylcyclopentadienylsilicon(II) cation, iPr5C5Si+, is obtained by reaction of the mixed silicocene (iPr5C5)(Me5C5)Si with H(OEt2)2+ Al[OC(CF3)3]4-.
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August 2004
Faculty of Chemistry, University of Bielefeld, Universitätsstrasse 25, D-33615 Bielefeld, Germany.
The reaction of decamethylsilicocene, (Me5C5)2Si, with the proton-transfer reagent Me5C5H2+B(C6F5)4- produces the salt (Me5C5)Si+ B(C6F5)4(2), which can be isolated as a colorless solid that is stable in the absence of air and moisture. The crystal structure reveals the presence of a cationic pi complex with an eta5-pentamethylcyclopentadienyl ligand bound to a bare silicon center. The 29Si nuclear magnetic resonance at very high field (delta = - 400.
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