How Changing the Bridgehead Can Affect the Properties of Tripodal Ligands

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  • Alex J. Plajer
    Department of Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UK
  • Annie L. Colebatch
    Department of Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UK
  • Felix J. Rizzuto
    Department of Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UK
  • Patrick Pröhm
    Institut fuer Chemie und Biochemie Freie Universitaet Berlin Fabeckstr. 34–36 14159 Berlin Germany
  • Andrew D. Bond
    Department of Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UK
  • Raúl García‐Rodríguez
    GIR MIOMeT-IU Cinquima-Química Inorgánica Facultad de Ciencias Universidad de Valladolid Campus Miguel Delibes 47011 Valladolid Spain
  • Dominic S. Wright
    Department of Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UK

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<jats:title>Abstract</jats:title><jats:p>Although a multitude of studies have explored the coordination chemistry of classical tripodal ligands containing a range of main‐group bridgehead atoms or groups, it is not clear how periodic trends affect ligand character and reactivity within a single ligand family. A case in point is the extensive family of neutral tris‐2‐pyridyl ligands E(2‐py)<jats:sub>3</jats:sub> (E=C−R, N, P), which are closely related to archetypal tris‐pyrazolyl borates. With the 6‐methyl substituted ligands E(6‐Me‐2‐py)<jats:sub>3</jats:sub> (E=As, Sb, Bi) in hand, the effects of bridgehead modification alone on descending a single group in the periodic table were assessed. The primary influence on coordination behaviour is the increasing Lewis acidity (electropositivity) of the bridgehead atom as Group 15 is descended, which not only modulates the electron density on the pyridyl donor groups but also introduces the potential for anion selective coordination behaviour.</jats:p>

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