The mechanisms of the reactions between hydrido-complexes and diazonium salts. Part 2. The reactions of cis,mer-[RhHCl2(PEtPh2)3]
- 1 January 1985
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 2067-2077
- https://doi.org/10.1039/dt9850002067
Abstract
The mechanisms of the reactions between cis,mer-[RhHCl2(PEtPh2)3] and (p-R′C6H4N2)BF4(R′= Cl, Me, or MeO) have been investigated in both methanol and acetonitrile. The influence of acid, chloride, and the para substituent on the aryl group defines a mechanism common to both solvents. Upon dissolution of cis,mer-[RhHCl2(PEtPh2)3], the solvento-species [RhHCl2(PEtPh2)2(solvent)] is formed rapidly. Subsequent substitution of the solvent molecule for the diazonium cation gives the intermediate [RhH(N2C6H4R′-p)Cl2(PEtPh2)2]+, in which the hydrido-group has been rendered sufficiently acidic that it is subsequently lost from the metal. Attack of chloride at the metal increases the basicity of the aryldiazenido-ligand sufficiently for it to be protonated and yield the aryldiazene product trans,mer-[Rh(NHNC6H4R′-p)Cl3(PEtPh2)2]. The various influences of isotopic substitution of the hydrido-group in cis,mer-[RhHCl2(PEtPh2)3] and in the acid have been explored for the reactions in acetonitrile.Keywords
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