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

By Stephen J. (Editor); Lippard


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VAN LEEUWEN 28 indicate that at room temperature a movement occurs in Ir(n-C,H,), similar to that shown in Fig. 16 for Rh(n-C,H,),. Movements of ally1 groups have also been observed in metal compounds containing other organic groups besides the ally1 group, for example, [(n-allyl),RhCI], (79,82), (C5H,)Mo(C0)2(n-allyl) (77), (OC)4BrW(n-C,H,) (90),and (n-C,H,),Fe(CO), (91). The preparation of [(allyl),RhCI], (allyl = I-rnethylallyl, 2-rnethylallyl, 2-chloroallyl) was reported by Powell and Shaw (79).

This takes place at lower temperature than the exchange with loss of configuration that can be seen in the NMR spectrum of the organic moiety. The former reaction was studied on the anion signals. b. Solutions of (Diene)MCI(L). The signals A and B obtained from solutions of the pure monomer have been subjected to NMR study. , (Nor)RhCI(AsPh,) (8), and proportional to the square root of the monomer concentration in other ones, for example, (C0D)lrCI(AsPh,) ( I I ) . In the first type of compound monomer-monomer exchange reactions occur, which may or may not proceed via a dimer intermediate: 1.

Furthermore, the dimer signals remain sharp. Rate measurements for various phosphines (12) showed that there is a reaction between (n-C,H,)PdCI (PR,) and dimer [(n-C,H,)PdCI], without exchange of PR, (75). The intermediate species 13 is probably trjnuclear and may involve splitting of one of the chlorine bridges in the dimer. Between -20" and +20" the signals of (1) and ( 2 ) also broaden and coalesce with those of (3) and (4) (65). Again, however, there is no exchange Lt 12 -c I Pd / \ r' 13 DYNAMIC ORGANOMETALIC COMPOUNDS 39 of PPh, between monomer and dimer as the dimer signals remain sharp.

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