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Extra info for Macromolecular physics - Crystal nucleation, growth, annealing
Example text
The lowest energy of the MLCT band occurs when the highest electron density is at the metal. The correlation thus strongly suggests that the rate of the reaction is primarily dependent on the energy of the filled d-orbitals on platinum. 3dm3 m o l - l s - l , in the order: R = Me > p-MeOC,H, > p-MeC,H, > rn-MeOC,H, > C,H, > p-FC,H, > p-ClC,H, > rn-CIC,H, (Jawad and Puddephatt, 1977). Interestingly, the - 44 SUNDUS HENDERSON AND RICHARD A. HENDERSON position of the MLCT band for R = p-MeC,H, is in about the same position as for o-MeC,H,, but this complex does not react with Me1 presumably because of the unfavourable steric interactions.
Changing the solvent from benzene to the more polar NMP and D M F does not affect these stereochemical results. , 1980) have led to the conclusion that the reactions of saturated alkyl halides (except methyl derivatives), vinyl and aryl halides and a-haloesters with trans-[IrCl(CO)(PR3)J proceed by a radical chain pathway, whereas methyl, benzyl and ally1 halides and a-haloethers probably react by a nucleophilic displacement process. One final type of coordinatively-unsaturated complex where stereochemical studies have demonstrated the nucleophilic character of the metal towards alkyl halides is [Pd(PR,),].
However, more detailed studies of the reactions between a variety of alkyl halides and trans-[IrCI(CO)(PR,),] has clarified this confused literature. , 1973; Labinger and Osborn, 1980). The contentious studies with trans-2-bromofluorocyclohexane were repeated with trans-[IrCI(CO)(PMe,),[ and the products isolated and purified fied. The correspondingly much improved 19F nmr spectrum (compared to the previous study) now demonstrated that two products were formed. Furthermore, the reaction of cis-2-bromofluorocyclohexane with trans[IrCI(CO)(PMe,),] yielded an identical 19Fspectrum clearly indicating that complete loss of stereochemistry at the carbon atom had occurred.