Inert Transition Metal Ion Complexes in Organic Synthesis: Protection and Activation

Single-crystal X-ray diffraction studies for a variety of metal ion complexes of functionalised sarcophagines (sarcophagine=sar=3,6,10,13,16,19-hexa-azabicyclo[6.6.6]icosane) have further confirmed not only that the form of the metal ion/sar unit is unique for each metal, albeit with a sensitivity of the conformation to the associated counter anions, but also that for any given metal and ligand substituent, the dimensions (bond lengths and angles) of the complex and the substituent at the secondary nitrogen centres do not differ significantly from those of the isolated components. Despite this, where the substituent contains reactive sites, the reactivity differs markedly from that of their form in an uncoordinated substrate. Rationalisations are offered for these differences, in part through the use of Hirshfeld surface analysis of the intermolecular interactions. The kinetic inertness of the complexes means that the metal ions can be considered to act as regioselective protecting groups.

Automated summary

Single-crystal X-ray diffraction studies have confirmed that the form of the metal ion/sarcophagine unit is unique for each metal, and the size and shape of the substituent on the complex do not differ significantly from those of the isolated components. However, reactivity differs when the substituent contains reactive sites. The use of Hirshfeld surface analysis helps explain these differences. The complexes act as kinetically inert regioselective protecting groups.