Oxidative addition of some geminal halonitroalkanes to iridium(I) and platinum(0) compounds |
| |
| Authors: | T.A.B.M. Bolsman J.A. Van Doorn |
| |
| Affiliation: | Koninklijke/Shell-Laboratorium, (Shell Research B.V.) Amsterdam The Netherlands |
| |
| Abstract: | Oxidative addition of 1-chloro-1-nitroethane to trans-IrCl(CO)-[P(CH3)2C6H5]2 followed by treatment of the initial product with pyridine yields a new iridium(III) complex IrCl(py)[COC(NO2)CH3][P(CH3)2C6H5]2, whose structure has been confirmed by X-rays crystallography. Two intermediate products have been observed by NMR spectroscopy; their structures have been tentatively assigned. The reaction of the corresponding bromine derivatives yields two isomers of the composition IrBr2(CO)[CH(NO2)CH3][P(CH3)2C6H5]2, and these are not affected by pyridine. The reaction of 1-chloro-1-nitroethane with Pt[P(C6H5)3]4 takes a completely different course in that yields nitrorethane and cis-PtCl2[P(C6H5)3]2 as the main products, with no detectable formation of the products of oxidation addition. A brief mechanistic investigation points towards the participation of radicals and radical anions as transient intermediates and a mechanism is proposed which explains most of the experimental results. |
| |
| Keywords: | |
| 本文献已被 ScienceDirect 等数据库收录！ |
