Isoelectronic caesium compounds: the triphosphenide Cs[tBu3SiPPPSitBu3] and the enolate Cs[OCH=CH2].
The caesium triphosphenide Cs[tBu3SiPPPSitBu3] was accessible from the reaction of CsF with the sodium triphosphenide Na[tBu3SiPPPSitBu3] in tetrahydrofuran at room temperature. In contrast to the preparation of tetrahydrofuran-solvated silanides M[SitBu3] (M = Li, Na, K), our efforts to synthesize the caesium silanide Cs[SitBu3] as a tetrahydrofuran complex failed. When tBu3SiBr was treated with an excess of caesium metal in tetrahydrofuran at room temperature, the caesium enolate Cs[OCH=CH2] and the supersilane tBu3SiH formed rather than the silanide Cs[SitBu3]. X-Ray quality crystals of the enolate Cs[OCH=CH2] (orthorhombic, Pnma) were obtained from tetrahydrofuran at ambient temperature. In contrast to the structures of its homologues M[tBu3SiPPPSitBu3] (M = Na, K), the caesium triphosphenide Cs[tBu3SiPPPSitBu3] features a polymer in the solid state (orthorhombic, Cmcm).
Lerner
Hans-Wolfram
HW
Institut für Anorganische Chemie, JW Goethe-Universität, Max-von-Laue-Str. 7, D-60438, Frankfurt, Germany. lerner@chemie.uni-frankfurt.de
Sänger
Inge
I
Schödel
Frauke
F
Lorbach
Andreas
A
Bolte
Michael
M
Wagner
Matthias
M