Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni II 2 (L)(μ 1,1 -N 3 )][ClO 4 ] (L = Macrocyclic N 6 S 2 Ligand)

Abstract : The dinuclear Ni-II complex [Ni-2(L-2)][ClO4](2) (3) supported by the 28-membered hexaaza-dithiophenolate macro-cycle (L-2)(2-) binds the N-3(-) ion specifically end-on yielding [Ni-2(L-2)(mu(1,1)-N-3)] [ClO4] (7) or [Ni-2(L-2)(mu(1,1)-N-3)][BPh4] (8), while the previously reported complex [Ni2L1(mu(1,3)-N-3)][ClO4] (2) of the 24-membered macrocycle (L-1)(2-) coordinates it in the end-to-end fashion. A comparison of the X-ray structures of 2, 3, and 7 reveals the form-selective binding of complex 3 to be a consequence of its preorganized, channel-like binding pocket, which accommodates the azide anion via repulsive CH center dot center dot center dot pi interactions in the end-on mode. In contrast to [Ni2L1(mu(1,3)-N-3)] [ClO4] (2), which features a S = 0 ground state, [Ni-2(L-2)(mu(1,1)-N-3)][BPh4] (8) has a S = 2 ground state that is attained by competing antiferromagnetic and ferromagnetic exchange interactions via the thiolato and azido bridges with a value for the magnetic exchange coupling constant J of 13 cm(-1) (H = -2JS(1)S(2)). These results are further substantiated by density functional theory calculations. The stability of the azido-bridged complex determined by isothermal titration calorimetry in MeCN/MeOH 1/1 v/v (log K-11 = 4.88(4) at I = 0.1 M) lies in between those of the fluorido- (log K-11 = 6.84(7)) and chlorido-bridged complexes (log K-11 = 3.52(5)). These values were found to compare favorably well with the equilibrium constants derived at lower ionic strength (I = 0.01 M) by absorption spectrophotometry (log K-11 = 5.20(1), 7.77(9), and 4.13(3) for N-3(-), F-, and Cl- respectively).
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Contributeur : Icmub - Université de Bourgogne <>
Soumis le : mardi 22 novembre 2016 - 11:16:55
Dernière modification le : vendredi 8 juin 2018 - 14:50:12

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Alexander Jeremies, Sina Gruschinski, Michel Meyer, Vitaly Matulis, Oleg A. Ivashkevich, et al.. Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni II 2 (L)(μ 1,1 -N 3 )][ClO 4 ] (L = Macrocyclic N 6 S 2 Ligand). Inorganic Chemistry, American Chemical Society, 2016, 55 (4), pp.1843 - 1853. ⟨http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b02743⟩. ⟨10.1021/acs.inorgchem.5b02743⟩. ⟨hal-01400603⟩

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