Tri(allyl) complexes of the heavy group 15 elements (M(C3H5)3; M = P–Bi) are liquid, air-sensitive compounds whose thermal stability drops with increasing molecular weight, from being able to tolerate distillation (P(C3H5)3, bp 69 °C/13 mm) to slowly decomposing at low temperatures, even in the dark (Bi(C3H5)3, –30 °C). The thermal stability of many allyl compounds can be improved by using substituted ligands, and this is especially true with the sterically demanding [1,3-(SiMe3)2C3H3]– (A´) allyl anion. We have employed this ligand in the generation of group 15 metal allyl complexes, both by using conventional salt metathesis in ether solvents, and with solid-state mechanochemical approaches. The latter has been used to investigate the role of solvents in the formation of the compounds, even though coordinated solvents are not present in the final products. The bulky allyls can lead to the formation of stereoisomeric forms of the group 15 complexes, whose relative abundance depends upon their method of synthesis. The synthesis and structures of these compounds will be discussed, as will be the implications for the use of mechanochemical techniques in expanding the boundaries of p-block organometallic chemistry.

Mechanochemical vs. solution syntheses of group 15 bulky allyl metal complexes

249th National Meeting (2015)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.