Synthesis and Crystal Structures of Sodium and Calcium Complexes with the Ligand <i>N</i>‐(2,6‐Dimethylphenyl)diphenylphosphinic Amide

Abstract

Abstract The sodium complex [{Ph 2 P(O)NH(2,6‐Me 2 C 6 H 3 )}Na{Ph 2 P(O)N(2,6‐Me 2 C 6 H 3 )}] 2 ( 2 ) with the ligand N ‐(2,6‐dimethylphenyl)diphenylphosphinic amide was synthesized involving the reaction of the neutral ligand [Ph 2 P(O)NH(2,6‐Me 2 C 6 H 3 )] ( 1 ) and sodium bis(trimethylsilyl)amide in toluene at 60 °C. The calcium complex [{Ph 2 P(O)NH(2,6‐Me 2 C 6 H 3 )CaI(THF) 3 }I] ( 3 ) was obtained by the reaction between the neutral ligand 1 and anhydrous calcium diiodide in THF at ambient temperature. The solid‐state structures of the complexes were established by single‐crystal X‐ray diffraction analysis. In the solid‐state structure of 2 , the sodium ion is coordinated through the chelation of oxygen atom attached to the phosphorus atom. Two different P–N and P–O bond lengths are observed, which indicates that one ligand moiety is anionic, whereas the second one is neutral. In the solid‐state structure of 3 , the calcium atom adopts distorted octahedral arrangement through the ligation of two phosphinic amide ligands, three THF molecules, and one iodide ion.