Reactivity of X₃P Compounds with Elemental Sulfur, Carbon Disulfide or Both, to Yield X₃PS, X₃P.CS₂ or X₃P.S_n.CS₂ Adducts

References

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• The exemple in Table I, entry 6 suggests that the thermodynamic stabilities of X3PS and X3P.S8 are similarly affected by the donor/acceptor properties of P. Also, the P-S bond order in X3PS grows with X in the order: C6H11 (1.32/-) < Me(1.35/1.41) < Ph (1.38/-) < Me2N (-/1.49) < MeO (-/1.69) < Cl (1.71/1.79) [estd. from the P-S bond lengths 31 (first value) or force constants 32-33(second value)]. Hence, the PIV form Ph3P+-S− appears to be dominant in Ph3PS and the PV form X3P=S in (EtO)3PS.
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• π-bonding (favouring the equatorial positions) is taken into account in this sequence. This effect is especially important for NR2 groups; it has also been recognised for SR and, to a lesser degree, for OR substituents.34,35
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• In terms of frontier orbitals, these irregularities should follow the changes of the energy gap E(LUMO)-E(HOMO), when going across a substitution series such as PhnP(OR)3-n – where the HOMO consists primarily of the lone pair on phosphorus [except for P(NR2)3 38] and the LUMO (for n < 3) is more or less based on the σ*(P-OR) antibonding orbital. Incidentally, the departures from additivity shown in Fig. 1 and 2 correspond to similar deviations of the 31P NMR chemical shift of X1X2X3P [ Van Wazer J. R. Letcher J. H. , in Topics in Phosphorus Chemistry , ed. Grayson M. Griffith E. J. ( John Wiley and Sons , 1967 ), Vol. 5 , p. 204 ].
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• Ph3P(SPh)(SSPh) and Ph3P(OEt)2, at least in their early geometry, are alleged to resemble the transition state, i.e. have (SPh)(SSPh) or (OEt)2 pairs in apical-equatorial positions. In principle, subsequent fluxional processes might afford isomers with all Ph equatorial, but only for Ph3P(OEt)2 would the gain in stability be significant; in this case, our line of reasoning still applies to the TS (kinetic control). The poor stability of (PriO)3P(OEt)2 (3 apicophilic OR groups in equatorial position) is probably the explanation as to why EtOOEt reacts faster with Ph3P than with P(OPri)3 (line M/Fig.4).
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