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Synthesis, Structure, Magnetic Properties and Phase Diagram of a

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Synthesis, Structure, Magnetic Properties and Phase Diagram of a

    # Supplementary Material (ESI) for Chemical Communications # This journal is ? The Royal Society of Chemistry 2003

    Supporting Information

    for the manuscript

    From metal to ligand electroactivity in nickel(II) oxamato complexes

    by

    aaaaaXavier Ottenwaelder, Rafael Ruiz-García, Geneviève Blondin, Rosa Carasco, Joan Cano,

    baaDoris Lexa, Yves Journaux and Ally Aukauloo*

a Laboratoire de Chimie Inorganique, UMR 8613, Université Paris-Sud, 91405 Orsay (France) b Laboratoire de Bioénergétique et Ingénierie des Protéines, 31 chemin Joseph Aiguier,

    13402 Marseille Cedex 20 (France).

    Content

Syntheses of ligands S2

    Syntheses of complexes S4

    Electrochemistry S4

     Fig S2: Cyclovoltammograms

    UV-Vis-NIR S6

     Fig S3: UV-Vis of the Ni(II) complexes 14.

    oxox Fig S4 and Table S2: UV-Vis-NIR of the oxidized complexes 14.

    References S7

    S1

    # Supplementary Material (ESI) for Chemical Communications # This journal is ? The Royal Society of Chemistry 2003

    Synthesis of ligands: All ligands were isolated as their diethyl esters, noted EtH-XL. The proligand 222123with X = H and compounds 4,5-dinitroveratrole and 4,5-diamino-1,2-dinitrobenzene have already been described.

    XXXXHNNH22,X = NO2X = NOH, Me2

    , Pd/CHClOEt2

    MeOHOOOOOONHHNNNHNHHNH2293 %THF

    88?0 %OOEtEtOOOOEtEtOO

    (CHO)AcOHClOEt2nDMFNaBHCN70 %378 %OO

    MeOOOONNMe22

    H, Pd/C2

    MeOH

    100 %OOHONNONNHNHHN2222

    OOEtEtOO

    XXĞXXĞ2 1) 4 OH2+2) Ni+2 PPh43) 2 PPhCl4

    OOOONHHNNN58?2 %Ni

    OOEtEtOOOOOO

    EtH-(X)L14222

X = Me, NO: To a solution of the corresponding 4,5-disubstitued o-phenylenediamine (10 mmol) in 2

    THF (100 mL) was added ethyl oxalyl chloride (2.7 mL, 24 mmol). The mixture was then refluxed for

    30 min, filtered to remove any insoluble material and evaporated to dryness. Addition of water to the

    resulting oil gave a solid that was filtered off, well washed with water and diethyl ether, and finally dried

    under vacuum. If necessary, this solid was then purified by flash-chromatography over silica with a

    dichloromethane methanol (9:1) eluant. X = Me (white solid, 2.96 g, 88%): CHNO (336.4): 1620261calcd. C, 57.14; H, 5.99; N, 8.33; found: C, 56.98; H, 5.87; N, 8.28. H NMR (CDCl): ; = 1.39 (t, 3

    6H, CH of ethyl), 2.22 (s, 6H, CH on the benzene ring), 4.37 (q, 4H, CH), 7.33 (s, 2H, aromatic), 33219.19 (s, 2H, NH). IR (KBr): = 3263 (NH), 1732, 1712 and 1672 cm (C=O). X = NO (light brown 2

    solid, 3.58 g, 90%): CHNO (398.3): calcd. C, 42.22; H, 3.54; N, 14.07; found: C, 41.78; H, 3.49; 1414410

    S2

# Supplementary Material (ESI) for Chemical Communications

    # This journal is ? The Royal Society of Chemistry 2003

    1N, 13.70. H NMR (CDCl): ; = 1,42 (t, 6H, CH), 4.43 (q, 4H, CH), 8.42 (s, 2H, aromatic), 9.63 (s, 33212H, NH). IR (KBr): = 3293 (NH), 1753, 1737, 1712 and 1696 cm (C=O), 1527 (broad, NO). 2

    X = OMe:

    a) diamine. This synthesis has been carried out under inert atmosphere. A suspension of 4,5-

    2dinitroveratrole (5.1 g, 22.4 mmol) and 10% Pd / C (500 mg) in methanol (200 mL) was stirred overnight under a high presure atmosphere of dihydrogen (40 bar). The mixture was then filtered over celite and well washed with methanol until the filtrate was colorless. After removal of the solvent,

    1colorless crystals of 4,5-diaminoveratrole covered by a deep green oxidation product were collected. H

    NMR (degased [D]DMSO): ; = 3.57 (s, 6H, CH), 4.09 (s, 4H, NH), 6.25 (s, 2H). IR: 3417, 3352 632

    and 3222 (NH).

    b) Proligand. This solid material was then dissolved in DMF (100 mL) and excess ethyl oxalyl chloride (7 mL, 60 mmol) was added. The brown solution was stirred at 90?C for 15 min and diisopropylethylamine (11 mL, 63 mmol) was added. After further 15 min at 90?C, the solution was cooled and filtered under air. After removal of the solvent and addition of water, a light brown precipitate formed which was filtered off. This solid was then purified by flash-chromatography over silica eluted with a dichloromethane methanol (5:1) mixture. The light-yellow solution was collected

    and evaporated to dryness. The white, slightly orange solid was collected with pentane and dried under vacuum (6.4 g, 78%). CHNO (368.4): calcd. C, 52.17; H, 5.47; N, 7.61; found: C, 52.29; H, 16202815.49; N, 7.57 H NMR (CDCl): ; = 1.40 (t, 6H, CH), 3.85 (s, 6H, OCH), 4.39 (q, 4H, CH), 7.11 33321(s, 2H, aromatic H), 9.16 (s, 2H, NH) IR (KBr): = 3328 and 3266 (NH), 1748, 1731 and 1688 cm

    (C=O).

    X = NH: A suspension of solid EtH-(NO)L (3.43 g, 8.6 mmol) and 10% Pd / C (350 mg) in 22222

    methanol (200 mL) was stirred overnight under a 40 bar atmosphere of dihydrogen. The mixture was then filtered over Celite and copiously washed with methanol. The solution was then evaporated to give a yellow solid that was collected with diethyl ether and conserved under vacuum (2.71 g, 93%).

    1CHNO (338.3): calcd. C, 49.70; H, 5.36; N, 16.56; found: C, 49.46; H, 5.39; N, 16.66 H NMR 1418466(DMSO-d): ; = 1.28 (t, 6H, CH), 4.26 (q, 4H, CH), ), 4.73 (s, 2H, NH), 6.65 (s, 2H, aromatic), 9.95 3221(s, 2H, NH) IR (KBr): = 3231, 3361 and 3434 (NH), 1690, 1724 and 1761 cm (C=O).

    4X = NMe: To a suspension of paraformaldehyde (1.33 g, 44 mmol) in glacial acetic acid (45 mL) 2

    under inert atmosphere was added solid EtH-(NH)L (1.50 g, 4.4 mmol). Then, solid sodium 2222

    cyanoborohydride (1.4 g, 22 mmol) was added portionwise to the stirred mixture. The suspension was degased and left for 15 h under stirring. The solution was then filtered and evaporated to dryness, resulting in a yellow oil to which were added successfully dichloromethane (50 mL) and water (50 mL). After several extractions, the combined yellow organic layers were washed three times with water and dried over anhydrous sodium sulfate. Evaporation to dryness yielded a yellow oil which was flash-chromatographied over silica eluted with dichloromethanemethanol (2-5% in MeOH). The desired

    product was precipitated with pentane from a solution in the minimum amount of dichloromethane. This yellow solid was then dried under vacuum (1.22 g, 70%). CHNO (394.4): calcd. C, 54.81; H, 18264616.64; N, 14.20; found: C, 54.82; H, 6.47; N, 14.24. H NMR (CDCl): ; = 1.40 (t, 6H, CH