In the present article, we report the synthesis of magnesium, calcium, and zinc complexes derived from the selenoether ligand Ph 2 P (S) NH–C 6 H 4 –SePh (1). The deprotonation of ligand 1 utilizing metal silylamides MN (SiMe 3) 2 2 (M = Mg, Ca, and Zn) conducted in tetrahydrofuran (THF) employing a 2: 1 molar proportion of ligand‐to‐metal enables the synthesis of their respective complexes, namely κ 2 N, S (Ph 2 P (S) N–C 6 H 4 SePh) κ 3 N, S, Se (Ph 2 P (S) N–C 6 H 4 SePh) Mg– (THF) (1a), Ph 2 P (S) N–C 6 H 4 SePh 2 Ca (1b), and κ 2 N, Se Ph 2 P (S) N–C 6 H 4 SePh 2 Zn (1c) in excellent yield proceeded via elimination of hexamethyldisilazane HN (SiMe 3) 2. Single crystal X‐ray diffraction analysis unambiguously revealed that ligand 1 exhibits three distinct coordination modes, κ ‐ (N, S), κ ‐ (N, Se), and κ‐ (N, S, Se), toward the metal centers. This coordination flexibility leads to a distorted octahedral geometry around the magnesium ion in complex 1a, whereas the zinc center in complex 1c adopts a distorted tetrahedral geometry in the solid state. In solution, the complexes were comprehensively characterized by multinuclear NMR spectroscopy (1 H, 13 C 1 H, and 31 P 1 H). Collectively, these findings expand the structural and spectroscopic understanding of closed‐shell metal complexes and highlight the versatility of the selenoether ligand in accessing structurally well‐defined coordination environments.
Sharma et al. (Mon,) studied this question.