New multidentate heteroscorpionate ligands: N-Phenyl-2,2-bis(pyrazol-1-yl)thioacetamide and ethyl 2,2-bis(pyrazol-1-yl)dithioacetate as well as their derivatives |
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Authors: | Run-Yu Tan Miao Du |
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Institution: | a Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, PR China b College of Chemistry and Life Science, Tianjin Normal University, Tianjin 300074, PR China |
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Abstract: | New multidentate heteroscorpionate ligands, N-phenyl-2,2-bis(3,5-dimethylpyrazol-1-yl)thioacetamide PhHNCSCH(3,5-Me2Pz)2 (1), N-phenyl-2,2-bis(3,4,5-trimethylpyrazol-1-yl)thioacetamide PhHNCSCH(3,4,5-Me3Pz)2 (2), and ethyl 2,2-bis(3,5-dimethylpyrazol-1-yl)dithioacetate EtSCSCH(3,5-Me2Pz)2 (8), have been synthesized and their coordination chemistry studied. These heteroscorpionate ligands can act as monodentate, bidentate, or tridentate ligands, depending on the coordinate properties of different metals. Reaction of W(CO)6 with 1 or 2 under UV irradiation yields monosubstituted carbonyl tungsten complexes W(CO)5L (L = 1 or 2), in which N-phenyl-2,2-bis(pyrazol-1-yl)thioacetamide acts as a monodentate ligand by the s-coordination to the tungsten atom. In addition, these monosubstituted tungsten complexes have also been obtained by heating ligand 1 or 2 with W(CO)5THF in THF. While similar reaction of Fe(CO)5 with 1, 2, or 8 under UV irradiation results in tricarbonyl iron complexes PhHNCSCH(3,5-Me2Pz)2Fe(CO)3 (5), PhHNCSCH(3,4,5-Me3Pz)2Fe(CO)3 (6), and EtSCSCH(3,5-Me2Pz)2Fe(CO)3 (9), respectively, in which N-phenyl-2,2-bis(pyrazol-1-yl)thioacetamide or ethyl 2,2-bis(pyrazol-1-yl)dithioacetate acts as a bidentate ligand through one pyrazolyl nitrogen atom and the CS π-bond in an η2-C,S fashion side-on bonded to the iron atom to adopt a neutral bidentate κ2-(π,N) coordination mode. Treatment of the lithium salt of 1 with Co(ClO4)2 · 6H2O gives complex PhNCSCH(3,5-Me2Pz)2]2Co(ClO4) with the oxidation of cobalt(II) to cobalt(III), in which N-phenyl-2,2-bis(3,5-dimethylpyrazol-1-yl)thioacetamide acts as a tridentate monoanionic κ3-(N,N,S) chelating ligand by two pyrazolyl nitrogen atoms and the sulfur atom of the enolized thiolate anion. |
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Keywords: | Bis(pyrazol-1-yl)methane Heteroscorpionate ligand Tungsten carbonyl Iron carbonyl Cobalt complex |
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