ISSN:
0044-2313
Keywords:
Tris(di-tert-butylphospha)heptaphosphanortricyclane, (t-Bu2P)3P7
;
Tris(di-tert-butylstiba)heptaphosphanortricyclane, (t-Bu2Sb)3P7
;
syntheses
;
crystal structure
;
31{1H} n.m.r. data
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
[t-Bu2P]3P7 and (t-Bu2Sb)3P7, as well as Investigations on the Formation of Heptaphosphanes (3) Containing PMe2, PF2, and P(CF3)2 GroupsTris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu2P)3P7 1 obtained by reacting Li3P7 · 3 DME with t-Bu2PF forms yellow crystals. (t-Bu2Sb)3P7 2 produced similarly from t-Bu2SbCl and Li3P7 · 3 DME didn't form crystals; it decomposes in a solution of toluene above -10°C. Both compounds were identified by their 31P{1H} NMR spectra, and 1 also by elemental analysis and single crystal structure determination (space group) P21/a, a = 1 712.0(9) pm, b = 1 105.1(7) pm, c = 1 854.0(10) pm, β = 94.96(4)°, Z = 4 formula units in the elementary cell).Attempts to synthesize (Me2P)3P7 3, (F2P)3P7 4 and [(F3C)2P]3P7 5 failed as dialkylchlorophosphanes as Me2PCl e. g. with Li3P7 · 3 DME react under Li/Cl exchange, dialkylfluorophosphanes (except t-Bu2PF) disproportionate, and neither PF3 nor (F3C)2PBr with Li3P7 · 3 DME give the desired products 4 or 5, resp.
Notes:
Tris(di-tert-butyl-phospha)-heptaphosphanortricyclan (t-Bu2P)3P7 1 entsteht durch Umsetzung von Li3P7 · 3 DME mit t-Bu2PF und bildet gelbe Kristalle. Das analog aus t-Bu2SbCl und Li3P7 · 3 DME gebildete (t-Bu2Sb)3P7 2 wurde nicht kristallin erhalten. Es zersetzt sich in Lösung (Toluol) oberhalb -10°C. Der Nachweis von 2 erfolgt über das 31P{1H}-NMR-Spektrum, der von 1 anhand des 31P{1H}-NMR-Spektrums, der Analyse und der Kristallstrukturbestimmung. 1 kristallisiert in der Raumgruppe P21/a mit Z = 4 Formeleinheiten; a = 1 712,0(9) pm, b = 1 105,1(7) pm, c = 1 854,0(10) pm, β = 94,96(4)°.Untersuchungen zur Bildung von (Me2P)3P7 3, (F2P)3P7 4, [(F3C)2P]3P7 5 führten nicht zum Ziel, weil Dialkylchlorphosphane wie Me2PCl (zur Bildung von 3) mit Li3P7 · 3 DME unter Li/Cl-Austausch reagieren, Dialkylfluorphosphane (ausgenommen t-Bu2PF) disproportionieren und PF3 sowie (F3C)2PBr mit Li3P7 · 3 DME nicht zu den Verbindungen 4 und 5 führen.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19915940105
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