Cobalt(II) Complexes with N‐Thioacylamidophosphates and 2,2′‐Bipyridyl and 1,10‐Phenathroline. Crystal Structures, Solution 1H NMR Spectral and Magnetic Properties

Abstract

AbstractStructure and magnetic properties of N‐diisopropoxyphosphorylthiobenzamide PhC(S)‐N(H)‐P(O)(OiPr)2 (HLI) and N‐diisopropoxyphosphoryl‐N′‐phenylthiocarbamide PhN(H)‐C(S)‐N(H)‐P(O)(OiPr)2 (HLII) complexes with the CoII cation of formulas [Co{PhC(S)‐N‐P(O)(OiPr)2}2] (1), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)2}2] (2), [Co{PhC(S)‐N(H)‐P(O)(OiPr)2}2{PhC(S)‐N‐P(O)(OiPr)2}2] (1a) and [Co{PhC(S)‐N‐P(O)(OiPr)2}2}(2,2′‐bipy)] (3), [Co{PhC(S)‐N‐P(O)(OiPr)2}2(1,10‐phen)] (4), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)2}2(2,2′‐bipy)] (5), [Co{PhN(H)‐C(S)‐N‐P(O)(OiPr)2}2(1,10‐phen)] (6) were investigated.Paramagnetic shifts in the 1H NMR spectrum were observed for high‐spin CoII complexes with HLI,II, incorporating the S‐C‐N‐P‐O chelate moiety and two aromatic chelate ligands. Investigation of the thermal dependence of the magnetic susceptibility has shown that the extended materials 1‐2 and 6 show ferromagnetic exchange between distorted tetrahedral (1, 2) or octahedral (1a, 6) metal atoms whereas 3 and 5 show antiferromagnetic properties. Compound 4 behaves as a spin‐canted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, Tc = 115 K. Complexes 1 and 1a were investigated by single crystal X‐ray diffraction. The cobalt(II) atom in complex 1 resides a distorted tetrahedral O2S2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. Complex 1a has a tetragonal‐bipyramidal structure, Co(Oax)2(Oeq)2(Seq)2, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in the typical 1,5‐O,S coordination mode. The ligands are in a trans configuration.