Premium
Rich Magnetic Chemistry of Cobalt(II) Complexes with N ‐Phosphorylthioureas. Crystal Structure and Solution 1 H NMR Spectral Properties
Author(s) -
Safin Damir A.,
Mlynarz Piotr,
Sokolov Felix D.,
Kubiak Maria,
Hahn F. Ekkehardt,
Babashkina Maria G.,
Zabirov Nail G.,
Galezowska Joanna,
Kozlowski Henryk
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700185
Subject(s) - chemistry , crystallography , antiferromagnetism , cobalt , crystal structure , deprotonation , paramagnetism , moiety , ferromagnetism , magnetic susceptibility , atom (system on chip) , metal , stereochemistry , inorganic chemistry , condensed matter physics , physics , ion , organic chemistry , computer science , embedded system
Structure and magnetic properties of Co II complexes with N ‐phosphorylthiourea derivatives {RC(S)NHP(O)(O i Pr) 2 } ( HL ) [Co{Et 2 NC(S)NP(O)(O i Pr) 2 } 2 ] ( 1 ), [Co{ i PrNHC(S)NP(O)(O i Pr) 2 } 2 ] ( 2 ), [Co{[ t BuNHC(S)NP(O)(O i Pr) 2 } 2 ] ( 3 ), [Co{p‐MeOC 6 H 4 NHC(S)NP(O)(O i Pr) 2 } 2 ] ( 4 ), [Co{p‐BrC 6 H 4 NHC(S)NP(O)(O i Pr) 2 } 2 ] ( 5 ) were investigated. Paramagnetic shifts in the 1 H NMR spectrum were observed for high‐spin Co II complexes with HL , incorporating amidophosphate moiety C(S)NP(O). The thermal dependence of the magnetic susceptibility has shown that the extended materials 2 , 3 and 5 show ferromagnetic exchange between distorted tetrahedral metal atoms, while in complex 4 antiferromagnetic behavior takes place. Compound 1 behaves as a spin‐canted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, T c = 175 K. Complex 2 was investigated by single crystal X‐ray diffraction. The cobalt(II) atom in complex 2 is in distorted tetrahedral CoO 2 S 2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands.