Cobalt(II) Complexes with N‐Thioacylamidophosphates and 2,2′‐Bipyridyl and 1,10‐Phenathroline. Crystal Structures,Solution 1H NMR Spectral and Magnetic Properties |
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| Authors: | Damir A. Safin Dr. Piotr Mlynarz F. Ekkehardt Hahn Prof. Dr. Maria G. Babashkina Felix D. Sokolov Nail G. Zabirov Joanna Galezowska Henryk Kozlowski |
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| Affiliation: | 1. Kazan/Russian Federation, A. M. Butlerov Chemistry Institute, Kazan State University;2. Münster/Germany, Institut für Anorganische und Analytische Chemie der Westf?lischen Wilhelms‐Universit?t;3. Damir A. Safin, Kremlevskaya str. 18, Kazan, 420008/Russian Federation, Fax: (007)8432543734, Tel: (007)8432315397;4. F. Ekkehardt Hahn, Inst. für Anorg. und Anal. Chemie, Corrensstrasse 36, D‐48149 Münster, Fax: (0049)2518333108, Tel: (0049)2518333110;5. Wroclaw/Poland, University of Technology;6. Wroclaw/Poland, University of Wroclaw |
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| Abstract: | 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. |
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| Keywords: | Amidophosphates Chelate Cobalt Magnetic properties NMR spectroscopy |
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