Coordination of iPr2P(O)NHP(O)iPr2 to Co(II): Simultaneous formation of octahedral and tetrahedral complexes

The reaction of iPr2P(O)NHP(O)iPr2 with CoCl2 ∙ 6H2O affords simultaneously the neutral tetrahedral [Co[iPr2P(O)NHP(O)iPr2-O,O′]Cl2] and the ionic octahedral [Co[iPr2P(O)NHP(O)iPr2-O,O′]3][CoCl4] complexes. These Co(II) complexes, which are stable towards oxidation to Co(III) species, self-assemble via N-H···Cl hydrogen bonds into a “honeycomb” (6,3) network. The structural flexibility of iPr2P(O)NHP(O)iPr2 that can accommodate both tetrahedral and octahedral geometries is discussed.