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Structure and magnetic properties of N-diisopropoxyphosphorylthiobenzamide PhC(S)-N(H)-P(O)(OiPr) 2 (HL I) and N- diisopropoxyphosphoryl-N′-phenylthiocarbamide PhN(H)-C(S)-N(H)-P(O)(OiPr) 2 (HL II) complexes with the Co II 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 Co II complexes with HL I,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 (la, 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, T c = 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 O 2S 2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. Complex la has a tetragonal-bipyramidal structure, Co(O ax) 2(O eq) 2(S eq) 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. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

Structure and magnetic properties of CoII complexes with N-phosphorylthiourea derivatives [RC(S)NHP(O)(OiPr)2] (HL) [Co {Et2NC(S)NP(O)(OzPr)2}2] (1), [Co [(PrNHC(S)NP(O)-(OiPr)2}2] (2), [Co {[/BuNHC(S)NP(O)(OiPr) 2}2] (3), [Co{p-MeOC6H4NHC(S)NP(O) (O(Pr)2}2] (4), [Co{P-BrC6H4NHC-(S) NP(O)(O(Pr)2}2] (5) were investigated. Paramagnetic shifts in the 1H NMR spectrum were observed for high-spin CoII 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 spincanted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, Tc = 175 K. Complex 2 was investigated by single crystal X-ray diffraction. The cobalt(II) atom in complex 2 is in distorted tetrahedral CoO2S2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

Thiourea, PhNHC(S)NHP(O)(OPri)2 (LH) chelates of CoII, NiII, and PdII ions have been obtained and investigated by single-crystal X-ray diffraction, UV, IR, NMR spectroscopy, and EI mass-spectrometry. The unusual 1,3-N,S-coordination via sulfur and NP(O) nitrogen atoms has been found in the trans-square-planar NiL2 and PdL2 complexes, whereas the 1,5-O,S-coordination is realized in the tetrahedral CoL2 complex. DFT calculations have revealed significant stabilization of the 1,3-N,S-structures due to stronger crystal field and the NH-O{double bond, long}P hydrogen bonds. © 2006 Elsevier B.V. All rights reserved.

Structure and magnetic properties of CoII complexes with N-phosphorylthiourea derivatives [RC(S)NHP(O)(OiPr)2] (HL) [Co {Et2NC(S)NP(O)(OzPr)2}2] (1), [Co [(PrNHC(S)NP(O)-(OiPr)2}2] (2), [Co {[/BuNHC(S)NP(O)(OiPr) 2}2] (3), [Co{p-MeOC6H4NHC(S)NP(O) (O(Pr)2}2] (4), [Co{P-BrC6H4NHC-(S) NP(O)(O(Pr)2}2] (5) were investigated. Paramagnetic shifts in the 1H NMR spectrum were observed for high-spin CoII 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 spincanted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, Tc = 175 K. Complex 2 was investigated by single crystal X-ray diffraction. The cobalt(II) atom in complex 2 is in distorted tetrahedral CoO2S2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

Structure and magnetic properties of N-diisopropoxyphosphorylthiobenzamide PhC(S)-N(H)-P(O)(OiPr) 2 (HL I) and N- diisopropoxyphosphoryl-N′-phenylthiocarbamide PhN(H)-C(S)-N(H)-P(O)(OiPr) 2 (HL II) complexes with the Co II 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 Co II complexes with HL I,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 (la, 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, T c = 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 O 2S 2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. Complex la has a tetragonal-bipyramidal structure, Co(O ax) 2(O eq) 2(S eq) 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. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

Thiourea, PhNHC(S)NHP(O)(OPri)2 (LH) chelates of CoII, NiII, and PdII ions have been obtained and investigated by single-crystal X-ray diffraction, UV, IR, NMR spectroscopy, and EI mass-spectrometry. The unusual 1,3-N,S-coordination via sulfur and NP(O) nitrogen atoms has been found in the trans-square-planar NiL2 and PdL2 complexes, whereas the 1,5-O,S-coordination is realized in the tetrahedral CoL2 complex. DFT calculations have revealed significant stabilization of the 1,3-N,S-structures due to stronger crystal field and the NH-O{double bond, long}P hydrogen bonds. © 2006 Elsevier B.V. All rights reserved.