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Inne
Cobalt(II) complexes with N-thioacylamidophosphates and 2,2'-bipyridyl and 1,10-phenathroline. Crystal structures, solution1H NMR spectral and magnetic properties.
Autorzy
Rok wydania
2007
Czasopismo
Zeitschrift für Anorganische und Allgemeine Chemie
Numer woluminu
633
Strony
1472-1479
DOI
10.1002/zaac.200700122
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Structure 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.
Adres publiczny
https://doi.org/10.1002/zaac.200700122
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