SUPERSILYL-CONTAINING PHOSPHORUS-COMPOUND S .3. FORMATION AND CHARACTERIZATION OF THE DISODIUM TETRAPHOSPHENEDIIDE(TBU(3)SI)NAP-P=P-PNA(SITBU(3)) AND OF ITS DIMER

Citation
N. Wiberg et al., SUPERSILYL-CONTAINING PHOSPHORUS-COMPOUND S .3. FORMATION AND CHARACTERIZATION OF THE DISODIUM TETRAPHOSPHENEDIIDE(TBU(3)SI)NAP-P=P-PNA(SITBU(3)) AND OF ITS DIMER, Chemische Berichte, 130(1), 1997, pp. 135-140
Citations number
25
Categorie Soggetti
Chemistry
Journal title
ISSN journal
00092940
Volume
130
Issue
1
Year of publication
1997
Pages
135 - 140
Database
ISI
SICI code
0009-2940(1997)130:1<135:SPS.FA>2.0.ZU;2-2
Abstract
Reaction of P-4 in THF or DME with 2 RNa (R* = SitBu(3)) at -78 degre es C leads quantitatively to deep red THF or DME adducts of RNaP-P=P- PNaR (3). According to P-31 NMR, the P-4 skeleton 3 is cis-configurat ed. On the other hand, reaction of P-4 in TBME with 2 RNa at -78 degr ees C leads quantitatively to (RNaP)(4)P-4 (4), a [2+2] cycloadduct o f 3, the Na4P8 skeleton of which according to X-ray structure analysis forms a double cube with four P atoms in the second layer and two P a nd two Na atoms in alternating positions in the first and in the third layer (the Na atoms are coordinated with donors). By resolving the TH F adduct 3 in TBME (the TBME adduct of 4 in THF) the compound 4 (the c ompound 3) is rapidly formed under reversal of the P-P=P-P configurati on by way of [2+2] cycloaddition (by way of [2+2] cycloreversion). 3 a nd 4 are sensitive to oxidation and to protolysis. With TONE, 3 is oxi dized to RP-2(4) (bicyclic P-4 skeleton), with CF3SO3H, 3 may be tran sformed into R3P5Na2 x 4 THF or in (R*P-3)(3) and R*PH2.