Alkyl Shifts between Transition Metals and Coordinated Main Group Atoms

✍ Scribed by J. V. Ortiz; Zdenêk Havlas; Roald Hoffmann

• Publisher: John Wiley and Sons
• Year: 1984
• Tongue: German
• Weight: 660 KB
• Volume: 67
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19840670102

✦ Synopsis

This work considers the theoretical aspects of the shift of an alkyl (or aryl) group from a coordinated phosphine to the 16-electron d8 transition metal to which it is coordinated. This rearrangement at first seems to resemble an anionic [1,2]-sigmatropic shift. But a detailed analysis of the relatively low barrier calculated for the reaction shows how all traces of the forbiddeness of the reaction have vanished. Phenyl migration should be still more facile. We also analyze in some detail the possible pathways of alkyl halide addition to a phenyl-Pt complex. An alkyl migration, now from metal to coordinated C-atom, could possibly intervene in this process. L Ph-Ni -Ph --7.32 --3.75 -12.02 --9.077 --5.475 --12.59 --21.40 --11.40 --18.60 -14.00 -17.30 -9.20 -17.80 -12.00 -26.00 -13.40 -13.60