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Supersilylverbindungen des Phosphors, V [1]. Darstellung, Struktur und Reaktivität des Pentaphosphids (tBu3Si)3P5Na2 und des Pentaphosphans (tBu3Si)3P5[2] / Supersilyl Compounds of Phosphorus, V [1]. Preparation, Structure, and Reactivity of the Pentaphosphide (tBu3Si)3P5Na2 and the Pentaphosphane (tBu3Si)3P5 [2]
-
Nils Wiberg
,
Angelika Wörner
Veröffentlicht/Copyright:
2. Juni 2014
The orange THF adduct (tBu3Si)3P5Na2 (THF)4 of the pentaphosphide (tBu3Si)3P5Na2 (3) has been prepared, (i) by protolysis of the tetraphosphide (tBu3Si)2P4Na2(THF)n (2) with CF3CO2H in THF (molar ratio 2 : 1 ) , (ii) by dissolving crystalline 2 in toluene, and (iii) by the reaction of P4 with tBu3SiNa(THF)2 in benzene (molar ratio 1 : 4). According to an X-ray structural analysis, the THF adduct of 3 contains a P3 ring with two PNa(SitBu3) substituents in cis position and one SitBu3 substituent in trans position to the former groups. The protolysis of 3 with CF3CO2H leads to the pentaphosphane P5H2(SitBu3)3 (9), the silylation of 3 with Me2SiCl2 to the pentaphosphane P5 (SiMe2)(SitBu3)3 (10), and the oxidation of 3 with C2(CN)4 to the pentaphosphane P5(SitBu3)3 (5). The structures of 3,5,9, and 10 have been assigned from 31P and 29Si NMR data. The pentaphosphane 5 contains a hitherto unknown P5 backbone of a P3 ring anellated with a P4 ring.
Received: 1998-4-17
Published Online: 2014-6-2
Published in Print: 1998-9-1
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Schlagwörter für diesen Artikel
Silicon;
Phosphorus;
Supersilyl;
Oligophosphides and -phosphanes;
NMR Data;
X-Ray Data
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