No abstract

Stable phosphiniminophosphonium salts of the hitherto unknown dimethyltetrafluorophosphate anion, [Me,P(N = PR3)2] + [Me2PF,] -, have been prepared in the reaction of dimethyltrifluorophosphorane with several N-trimethylsilylphosphine imines. THE spontaneous rearrangement of certain dialkylaminotrifluorophosphoranes, R1PF3NR22, with formation of the ionic products, [R1PF(NR2,),] [RPF,] , has been established

D(m) from diffusion experiments, and s(m) from experiments with the ultracentrifuge. The order of magnitude of the diffusion coefficient D is 10-5 cmZ/sec in this system, and that of s is 10-13 sec. Equation (65) applies to very dilute solutions of strong electrolytes containing two ionic species. In this case we can also apply the approximations Thus from Equations (65) and (79) we obtain in which M; is the equivalent weight of tk.e electrolyte, defined by and in which we have made use of (60) and(v2 is the partial specific volume of the electrolyte).In the limit m i 0, we find from Equations (81) and (79), together with Equations (66), (SO), and (83):In Equations (84) and (85), v! is the limiting value of the partial specific volume of the electrolyte at infinite dilution, and pol is the density of the pure solvent. The limiting law (85) is known as Svedberg's equation (Svedberg 1925), particularly under the condition -I == I , (nonelectrolyte solutions). This relationship can be used to determine the quantity M~/ v . Equation (85) can also be derived from Equations (67) and (84) using (60) and (82). Since the molecular theory of sedimentation is fundamentally simpler than that of diffusion, Equation (79) is useful in calculating D from s. On the other hand, D is the more easily measured quantity, so that (79) will also be used for the reverse calculation.

Die neuen P(III)‐Verbindungen (II), (IIIa) und (Vb‐e) die eine oder mehrere Hexafluorisopropoxy‐Gruppen enthalten, werden durch Umsetzung entsprechender P(III)‐halogenide mit dem Li‐hexafluorisopropoxid (I) synthetisiert.

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