Me thanolysis of 2-c yanopyr Me thanolysis of 2-c yanopyr idine in - PowerPoint PPT Presentation

Me thanolysis of 2-c yanopyr Me thanolysis of 2-c yanopyr idine in the idine in the c oor c oor dination sphe r dination sphe r e of mangane se (II). T e of mangane se (II). T he he str str uc tur uc tur e of Mn 4 L e of Mn 4 L 6 Cl 2 c luste r 6 Cl 2 c luste r (L (L = me thyl = me thyl pic olinimidate ) pic olinimidate ) c ía 1 , Ana M. Gonzále z-Noya 2 and c ía 1 , Ana M. Gonzále z-Noya 2 and ouc o 1 , R ouc o 1 , R ido 2 , M. Isabe l F ido 2 , M. Isabe l F L L ar ar a R a R osa Pe dr osa Pe dr e r e r nánde z-Gar nánde z-Gar o 1,* o 1,* Mar Mar c e lino Mane ir c e lino Mane ir Departamento de Química Inorgánica, Facultade de Ciencias, Universidade de Santiago de Compostela Departamento de Química Inorgánica, Facultade de Ciencias, Universidade de Santiago de Compostela 1 1 Departamento de Química Inorgánica, Facultade de Química, Universidade de Santiago de Compostela Departamento de Química Inorgánica, Facultade de Química, Universidade de Santiago de Compostela 2 2 Correspondence: Marcelino.maneiro@usc.es; Tel.: +34982824106 Correspondence: Marcelino.maneiro@usc.es; Tel.: +34982824106 * * Presented at the 22 nd International Conference on Synthetic Organic Chemisty, November 2018 . Presented at the 22 nd International Conference on Synthetic Organic Chemisty, November 2018 .

 Increased reactivities of molecules coordinated in  Increased reactivities of molecules coordinated in metal complexes have wide applications in chemistry. metal complexes have wide applications in chemistry. Manganese(II) complexes containing chelating N,N- Manganese(II) complexes containing chelating N,N- donor ligands are important due to their application in donor ligands are important due to their application in catalytic systems [1], antioxidant drugs [2-3], MRI catalytic systems [1], antioxidant drugs [2-3], MRI contrast agents [4], antibacterial [5], antifungal [6] contrast agents [4], antibacterial [5], antifungal [6] and nanomaterials [7]. The activation of ligands and nanomaterials [7]. The activation of ligands Intr Intr oduc tion oduc tion containing the nitrile group upon their coordination to containing the nitrile group upon their coordination to a manganese ion has been exploited in addition a manganese ion has been exploited in addition reactions of nucleophiles such as amines, alcohols reactions of nucleophiles such as amines, alcohols and water. and water.  The 2-cyanopyridine as a chelating bidentate ligand  The 2-cyanopyridine as a chelating bidentate ligand can be coordinated to manganese ion from two can be coordinated to manganese ion from two nitrogen atoms of pyridine ring and carbonitrile group nitrogen atoms of pyridine ring and carbonitrile group in the presence of non-protonic solvents. Reaction of in the presence of non-protonic solvents. Reaction of ds: manganese; methanolysis; ds: manganese; methanolysis; Ke ywor Ke ywor this chelating ligand with manganese(II) salts in this chelating ligand with manganese(II) salts in X-ray diffraction; supramolecular X-ray diffraction; supramolecular protonic solvents as methanol leads to the formation protonic solvents as methanol leads to the formation chemistry chemistry of complexes which contain O -methyl picolimidate. of complexes which contain O -methyl picolimidate. Although this type of process is already known, this Although this type of process is already known, this communication describes for the first time the synthesis communication describes for the first time the synthesis and complete characterization, including X-ray crystal and complete characterization, including X-ray crystal structure, of the resulting Mn 4 L 6 Cl 2 cluster, where L is structure, of the resulting Mn 4 L 6 Cl 2 cluster, where L is the O -methyl picolimidate ligand. the O -methyl picolimidate ligand.

 MS(ESI): m/z 1108.4 [ 1 + H + ] + , 1129.5 [ 1 + Na + ] + .  MS(ESI): m/z 1108.4 [ 1 + H + ] + , 1129.5 [ 1 + Na + ] + . Mate r Mate r ials and Me thods ials and Me thods Elemental analysis found: C, 45.1; H, 4.4; N, 14.9 %. Elemental analysis found: C, 45.1; H, 4.4; N, 14.9 %. C 42 H 48 Cl 2 Mn 4 N 12 O 6 (MW 1107.6) requires C,45.6; H, C 42 H 48 Cl 2 Mn 4 N 12 O 6 (MW 1107.6) requires C,45.6; H, 4.3; N, 15.2 %. IR (cm-1): IR (cm-1):  (N-H 4.3; N, 15.2 %. IR (cm-1): IR (cm-1):  (N-H 6 Cl 2 ( 1): To a CH 3 OH/H 2 O solution 6 Cl 2 ( 1): To a CH 3 OH/H 2 O solution 2 2 Mn 4 L Mn 4 L carboxamide) 3237 (m),  (C-H) Ar 3072 (m),  (C-H) Me carboxamide) 3237 (m),  (C-H) Ar 3072 (m),  (C-H) Me of 2-cyanopyridine (42 mg, 0.4 mmol) of 2-cyanopyridine (42 mg, 0.4 mmol) 2981 (w), 2940 (w),  ( C=NH carboxamide) 1659 (s), 2981 (w), 2940 (w),  ( C=NH carboxamide) 1659 (s), was added dropwise a methanol was added dropwise a methanol solution (40 mL) of MnCl 2 (40 mg, 0.2 solution (40 mL) of MnCl 2 (40 mg, 0.2  ( C=N) 1631 (s), ν [(N=C–O–) + δ (NH)] 1379 (s), δ (O–  ( C=N) 1631 (s), ν [(N=C–O–) + δ (NH)] 1379 (s), δ (O– mmol). The mixture turned light green. mmol). The mixture turned light green. CH3) 1206 (m), ν as(C–O–C) 1138 (s), ν s(C–O–C) 965 CH3) 1206 (m), ν as(C–O–C) 1138 (s), ν s(C–O–C) 965 It was heated for 40 min with stirring It was heated for 40 min with stirring (m),  (Mn-Cl) 303 (m). (m),  (Mn-Cl) 303 (m). and then filtered after cooling to room and then filtered after cooling to room temperature. Well-shaped colorless temperature. Well-shaped colorless crystals of 1 suitable for X-ray crystals of 1 suitable for X-ray diffraction were obtained within 2 diffraction were obtained within 2 months with a 25% yield upon slow months with a 25% yield upon slow evaporation of the solvents. Yield: 0.01 evaporation of the solvents. Yield: 0.01 g (20 %). Selected data for 1 : g (20 %). Selected data for 1 :

aphic studie s. Data for 1 were aphic studie s. Data for 1 were  X-r  X-r ay c r ay c r ystallogr ystallogr collected at room temperature on a Bruker Smart collected at room temperature on a Bruker Smart CCD-1000 diffractometer. Mo–K α radiation CCD-1000 diffractometer. Mo–K α radiation ( λ =0.71073 Å) from a fine-focus sealed tube source ( λ =0.71073 Å) from a fine-focus sealed tube source (at 100 K). The computing data and reduction (at 100 K). The computing data and reduction Mate r Mate r ials and Me thods ials and Me thods were made by BRUKER SAINT [8] software. An were made by BRUKER SAINT [8] software. An empirical absorption correction was applied using empirical absorption correction was applied using SADABS [9]. The structure was solved by SIR-97 [10] SADABS [9]. The structure was solved by SIR-97 [10] and refined by full-matrix least-squares techniques and refined by full-matrix least-squares techniques against F 2 using SHELXL-97 [11]. Positional and against F 2 using SHELXL-97 [11]. Positional and anisotropic atomic displacement parameters were anisotropic atomic displacement parameters were refined for all heteroatoms. The hydrogen atoms refined for all heteroatoms. The hydrogen atoms positions were included in the model by electronic positions were included in the model by electronic density, and they were refined isotropically [Uiso(H) density, and they were refined isotropically [Uiso(H) = 1.2Ueq(Atom)] or were geometrically calculated = 1.2Ueq(Atom)] or were geometrically calculated and refined using a riding model (isotropic thermal and refined using a riding model (isotropic thermal parameters 1.2–1.5 times those of their carrier parameters 1.2–1.5 times those of their carrier atoms). atoms).