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Abstract: Structural analysis of a previously reported half-sandwich complex having three-legged “piano-stool” geometry [(η6-C6H6)RuII(L1)Cl][PF6] (1) (L1 = 2-(pyrazol-1-ylmethyl)pyridine) is described. Treatment of 1 with (i) Ag(CF3SO3) in CH3CN and (ii) NaN3 in CH3OH, and (iii) the reaction between [(η6-C6H6)Ru(L2)Cl]-[PF6] (2) (previously reported) and NaCN in C2H5OH led to the isolation of [(η6-C6H6)Ru(L1)(CH3CN)][PF6]2 (3), [(η6-C6H6)Ru(L1)(N3)][PF6] (4), and [(η6-C6H6)Ru(L2)(CN)][PF6] (5), respectively (L2 = 2-(3,5-dimethyl-pyrazol-1-ylmethyl)pyridine). The complex [(η6-C6H6)Ru(L4)Cl][PF6] (6) with a new ligand (L4 = 2-[3-(4-fluorophenyl)pyrazol-1-ylmethyl]pyridine) has also been synthesized. The structures of 3–6 have been elucidated (1H NMR spectra; CD3CN). The molecular structures of 1, 4, and 6·C6H5CH3 have been determined. Notably, the crystal-packing in these structures is governed by C–H⋯X (X = Cl, N) interactions, generating helical architectures. [Copyright &y& Elsevier]

Abstract: We report on a detailed analysis of the thermal transition hysteresis loop and the relaxation curves of the recently investigated compound [FeII(L)2][ClO4]2 ·C7H8 [V. Mishra et al., Inorg. Chem. (2008)]. We developed a variant of a previous kinetic cooperative model, modified for including short-range and long-range Gaussian distributions of energy parameters. The resulting set of coupled master equations was solved numerically for the dynamic and the quasi-static case. We have elucidated the various correlations between the distribution widths and the long-range interaction parameter, which basically have opposite effects. It is shown that presence of a steep hysteresis loop may hide a sizable short-range distribution, while the stretched character of the relaxation curves may also hide the presence of strong interactions. We also show that the coherent analysis of the set of relaxation curves at different temperatures does not allow to disentangle properly all the relevant parameters. We discuss these data with respect to the other photomagnetic experiments, T(LIESST) curve and light-induced thermal hysteresis (LITH) loop, and finally we try to address the question of the real nature of the cooperative relaxation process. [Copyright &y& Elsevier]

Abstract: A full account of half-sandwich complexes of ruthenium(II) having three-legged “piano-stool” geometry supported by tridentate (2-pyridyl)alkylamine ligands is presented. Reaction of the dimer [{(η6-C6H6)RuCl(μ-Cl)}2] with N-methyl-N,N-bis(2-pyridylmethyl)amine (MeL∗) in CH3OH in the presence of NH4PF6 affords the complex [(η6-C6H6)Ru(MeL∗)][PF6]2 (1). A similar reaction with N-methyl-N,N-bis(2-pyridylethyl)amine (MeL∗∗), however, affords a non-organometallic Ru(III)-dimeric complex (5) (the composition of this complex has been established by physicochemical method). Nucleophilic addition reaction on 1 with NaBH4 leads to the isolation of a cyclohexadienyl complex [(η5-C6H7)Ru(MeL∗)][PF6] (3). The molecular structure of 1 ·2CH3CN, 3, and previously reported cyclohexadienyl complex [(η5-C6H7)Ru(MeL)][PF6] (4) [MeL=N-methyl-[(2-pyridyl)ethyl(2-pyridyl)-methyl]amine], obtained from the reaction between NaBH4 and previously reported “piano-stool” complex [(η6-C6H6)Ru(MeL)][PF6]2 (2), has been confirmed by X-ray crystallography. Solution-state structure of new complexes 1 and 3 has been elucidated by their 1H NMR spectra in CD3CN. The behavior of complex 3 has been investigated with the aid of two-dimensional 1H NMR spectroscopy, as well. An attempt has been made to provide a rationale for the effect of supporting tridentate N-donor ligand [MeL, MeL∗, and MeL∗∗], varying in the chelate ring-size on (i) the relative stability of half-sandwich η6-benzene Ru(II) complexes and (ii) the electrophilicity of Ru(II)-coordinated benzene ring on the nucleophilic addition reactions. [Copyright &y& Elsevier]

Abstract: Four half-sandwich ruthenium(II) complexes [(η6-C6H6)Ru(L1-O)][PF6] (1), [(η6-C6H6)Ru(L2-O)][PF6] (2), [(η6-C6H6)Ru(L3-O)][PF6] (3), [(η6-C6H6)Ru(L4-O)][PF6] (4a), and [(η6-C6H6)Ru(L4-O)][BPh4] (4b) [L1-OH, 4-nitro-6-{[(2′-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L2-OH, 2,4-di-tert-butyl-6-{[(2′-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L3-OH, 2,4-di-tert-butyl-6-{[2′-((pyridin-2-yl)benzylamino)methyl}-phenol; L4-OH, 2,4-di-tert-butyl-6-{[(2′-imethylaminoethyl)methylamino]methyl}-phenol (L4-OH)], supported by a systematically varied series of tridentate phenolate-based pyridylalkylamine and alkylamine ligands are reported. The molecular structures of 1–3, 4a, and 4b have been elucidated in solution using 1H NMR spectroscopy and of 1, 3, and 4b in the solid state by X-ray crystallography. Notably, due to coordination by the ligands the Ru center assumes a chiral center and in turn the central amine nitrogen also becomes chiral. The 1H NMR spectra exhibit only one set of signals, suggesting that the reaction is completely diastereoselective [1: S Ru,S N/R Ru,R N; 2: R Ru,R N/S Ru,S N; 3: S Ru,R N/R Ru,S N; 4b: S Ru,R N/R Ru,S N]. The crystal packing in 1 and 3 is stabilized by C–H…O interactions, in 4b no meaningful secondary interactions are observed. From the standpoint of generating phenoxyl radical, as investigated by cyclic voltammetry (CV), complex 1 is redox-inactive in MeCN solution. However, 2, 3, and 4a generate a one-electron oxidized phenoxyl radical coordinated species [2]2+ , [3]2+ , and [4a]2+ , respectively. The radical species are characterized by CV, UV–Vis, and EPR spectroscopy. The stability of the radical species has been determined by measuring the decay constant (UV–Vis spectroscopy). [Copyright &y& Elsevier]

Abstract: New series of half-sandwich ruthenium(II) complexes supported by a group of bidentate pyridylpyrazole and pyridylimidazole ligands [(η6-C6H6)Ru(L2)Cl][PF6] (1), [(η6-C6H6)Ru(HL3)Cl][PF6] (2), [(η6-C6H6)Ru(L4)Cl][PF6] (3), and [(η6-C6H6)Ru(HL5)Cl][PF6] (4) [L2, 2-[3-(4-chlorophenyl)pyrazol-1-ylmethyl]pyridine; HL3, 3-(2-pyridyl)pyrazole; L4, 1-benzyl-[3-(2′-pyridyl)]pyrazole; HL5, 2-(1-imidazol-2-yl)pyridine] are reported. The molecular structures of 1–4 both in the solid state by X-ray crystallography and in solution using 1H NMR spectroscopy have been elucidated. Further, the crystal packing in the complexes is stabilized by C–H⋯X (X=Cl and π), N–H⋯Cl, and π–π interactions. [Copyright &y& Elsevier]