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- Title
Activation of P<sub>4</sub> by Li[Si tBu<sub>3</sub>]: generation of lithium bis(supersilyl)heptaphosphanortricyclanide Li[P<sub>7</sub>(Si tBu<sub>3</sub>)<sub>2</sub>].
- Authors
Sänger, Inge; Breunig, Jens; Schödel, Frauke; Bolte, Michael; Lerner, Hans-Wolfram
- Abstract
Treatment of P4 with one equivalent of Li[Si tBu3] leads to the formation of a number of oligo-phosphanes and -phosphides, e.g. the bicyclo[1.1.0]tetraphosphane P4(Si tBu3)2, the heptaphosphanortricyclane P7(Si tBu3)3, the tetraphosphides Li3[P(PSi tBu3)3] (Li3 [2a]), and the pentaphosphacyclopentadienide Li[P5]. From this reaction we could isolate single crystals of Li3 [2a]. However, this reaction took another course in the presence of Li[OSi tBu3]. When P4 was treated with one equivalent of Li[Si tBu3] in the presence of Li[OSi tBu3], the heptaphosphanortricyclanide Li[P7(Si tBu3)2] (Li [8a]) was formed. Single crystals of the cluster {Li4(C6H6)(OSi tBu3) [8a]3}·C6H6 (orthorhombic, space group Pca21) were isolated from the reaction mixture at ambient temperature. This cluster compound consists of three chiral Li[P7(Si tBu3)2] units, one silanolate Li[OSi tBu3], and one benzene molecule. We further investigated the degradation reaction of the bicyclo[1.1.0]tetraphosphane P4(Si tBu3)2. After heating a benzene solution to 60 °C for 24 h, we found 100 % conversion of P4(Si tBu3)2, and P7(Si tBu3)3 (monoclinic, space group P21/ c) and tBu3SiPH2 were formed.
- Subjects
LITHIUM phosphide; SINGLE crystals; X-ray spectroscopy; NUCLEOPHILIC addition (Chemistry); BIOCHEMICAL substrates; STOICHIOMETRY
- Publication
Zeitschrift für Naturforschung B: A Journal of Chemical Sciences, 2016, Vol 71, Issue 2, p135
- ISSN
0932-0776
- Publication type
Article
- DOI
10.1515/znb-2015-0156