Complexes of N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2 (X = O, S) with cobalt(II), zinc(II), and cadmium(II). Crystal structure of Co[AdNHC(S)NP(S)(OiPr)2]2

Abstract

Reaction of the potassium salts of N-(thio)phosphorylated thioureas of common formula Ad-NHC(S)N(H)P(X)(OiPr) 2 (Ad = adamantyl; X = O, HL I ; X = S, HL II ) with Co(II), Zn(II), and Cd(II) cations in aqueous EtOH leads to M(L I,II -X, S) 2 chelate complexes. The Cd(II) complex Cd(L I ) 2 could not be isolated under analogous conditions because of its hydrolytic lability. The structure of the resulting compounds was studied by means of spectroscopy and microanalysis; in addition, the molecular structure of the complex Co(L II ) 2 was elucidated by single crystal X-ray diffraction analysis. The cobalt atom is in a tetrahedral S 4 environment formed by the C=S and P=S sulfur atoms of two deprotonated ligands L II . The magnetic properties of Co(L I,II ) 2 were investigated and the photoluminescent properties of the complexes are also reported.

Synthesis and characterization of crown ether–containing N‐phosphorylated thioureas RC(S)NHP(O)(OiPr)2 (R = 1‐aza‐15‐crown‐5, 1‐aza‐12‐crown‐4) and their Co(II) and Ni(II) complexes

“…These data indicate three unpaired electrons for Co(II). The magnetic moments of the Co(II) complexes at room temperature fall in the range 4–5 B.M., which is characteristic for mononuclear, high‐spin, tetrahedral Co(II) complexes with R′C(S)NHP(X)(OR) 2 (X = O, S) ligands 28–30. The diamagnetic character for the [ NiL I,II 2 ] complexes indicates the square‐planar arrangement.…”