Progress in Inorganic Chemistry, Volume 14; by Stephen J. (Editor); Lippard

By Stephen J. (Editor); Lippard

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Type ( I ) example is again the mixture of (n-C,H,)PdCl(PPh,) and (n-C,H,)Pd(OAc)(PPh,) where a rapid coalescenceof the two A B C D patterns occurs to one ABCD and not to a AA‘BB’ pattern. Type ( 2 ) examples are the phosphine monomer and dimer acetate mixture, and also the mixture of phenylmercury acetate and the n-allylpalladium-acetate-phosphine. In these examples fast coalescence of acetate signals occurs without left-right interchange. A similar case has been reported for (diene)Rh(acetate) (140).

24. Numbering of the sites. A t temperatures above -50" the C,H7 resonances broadened i n an asymmetric way. 57 h, which is at the weighted mean of the original low-temperature signals. A computersimulated line shape strongly indicated that the rearrangement involved is a sequence of I ,2-shifts. A relatively small percentage of I ,3-shifts may 53 DYNAMIC ORGANOMETALLIC COMPOUNDS occur, but I ,4-shifts were excluded. 8. The general feature of 1,2-shifts in all ring compounds rules out the possibility of 7t-c rearrangements of the type shown in Fig.

Several interesting features can be observed in the spectra, but attention will be paid here to the main points only. The IT-greaction of the acetate is not influenced by the addition of the chloride monomer, although at about 0°C the anion exchange becomes visible in the NMR spectrum. In this medium the exchange is presumably a concerted process involving a double anion bridge. Theconclusion here is that the formation of a double anion bridge between two monomers does not catalyze the 7c-o reaction.

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