Trispyrazolylmethane piano stool complexes of iron(II) and cobalt(II) |
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| Institution: | 1. Beijing National Laboratory for Molecular Sciences, China;2. CAS Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;3. National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;4. Beijing Mass Spectrometry Centre, China |
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| Abstract: | A series of cationic trispyrazolylmethane complexes of the general form TmRM(CH3CN)3]2+ (Tm = tris(pyrazolyl)methane, 1, R = 3,5-Me2, M = Fe(II); 2, R = 3-Ph, M = Fe(II); 3, R = 3,5-Me2, M = Co(II); 4, R = 3-Ph, M = Co(II)) with ‘piano-stool’ structures was prepared by the reaction of the N3tripodal ligands (TmR)with (CH3CN)6M](BF4)2 in a 1:1 stoichiometric ratio. Magnetic susceptibility measurements indicate that all four complexes with BF4? counter anions are paramagnetic, high-spin systems in the solid state with μeff at high temperatures of 5.2 (1, S = 2), 5.4 (2, S = 2), 4.9 (3, S = 3/2) and 4.6 (4, S = 3/2) BM, respectively. Comparisons of bond lengths from the metal centre to the TmR nitrogen donors, and from the metal centre to the acetonitrile nitrogen donors indicate that the neutral tripodal ligands appear to be more weakly coordinated to the metal centre than are the acetonitrile ligands. Reactions of these tripodal complexes with bidentate phosphine ligands, such as 1,2-diphosphinoethane or 1,2-bis(diallylphosphino)ethane leads to displacement of the tripodal ligand, or to the formation of more thermally stable bis-ligand complexes M(TmR)2 (R = 3,5-dimethyl). |
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