. Nicl2 and . 6h2o, 22 mmol, 54 mg) in MeOH (5 mL) was added followed 6 hours later by the addition of a solution of Ph4PBr (190 mg, 0.45 mmol) in MeOH (5 mL) After stirring for 15

, 60) for [Ph4P][Ni(MeS-tzdt)2] and from warm CH3CN for, Ph4P][Ni(EtS-tzdt)2] to afford the monoanionic salts as dark blue green crystals

, MeS-tzdt)2] Yield: 31 % (55 mg), Mp = 240°C. HRMS (ESI) Calcd for

, C8H6N2S8Ni: 443.76557 Found: 443.7657. Anal. Calcd. for C32H26N2NiPS8: C, 48.98; H

, Ph4P][Ni(EtS-tzdt)2] Yield: 62% (110 mg). Mp = 178°C. HRMS (ESI) Calcd for

C. , 7968 Found: 471.7969. Anal. Calcd. for C34H30N2NiPS8: C, 50.24; H, 3.72; N, 3.45%. Found: C, 50.62, pp.471-474

, A solution of Na (80 mg, 3.47 mmol) in MeOH (20 mL) was added to the dithiole-2-one 1 (300 mg, 1.14 mmol) After complete dissolution the solution was stirred for 30 mn at room temperature. Then a solution of NiCl2, pp.6-8

, MeOH (5 mL) was added followed 6 hours later by the addition of a solution of Ph4PBr

, After stirring for 15 h, the dark precipitate was filtered and recrystallized from CH2Cl2/MeOH (20/80) to afford monoanion [Ph4P][Ni(tBu-thiazdt)2] as dark red crystals, Yield: 68% (338 mg). Mp = 170°C (dec). HRMS (ESI) Calcd for

, C14 H18 N2 S8 58 Ni) : 527.85947 Found: 527.8598. Anal. Calcd. for C38H38N2PNiS8: C, pp.52-75

, Found: C, 51.75; H, 4.75, Crystals of the [PPh4][Ni(tBu-thiazdt)

, as toluene solvate were obtained through recrystallisation in CH3CN

, Ni(RS-tzdt)2] (route b) [PPh4][Ni(tBu-thiazdt)2] (20 mg, 0.023 mmol) was dissolved in 10

C. Ml, An excess of alkyliodide (1 mL, CH3I or CH3CH2I) was added to the reaction medium and the solution was refluxed for 2 h under inert atmosphere After cooling, a dark blue-greenish precipitate was formed. The solid was filtered and washed with dichloromethane affording the neutral, MeS-tzdt)2] complex in 64% yield and neutral [Ni(EtS-tzdt)2] complex in 5% yield

, Electrocrystallizations They were performed in two-compartment cells with Pt electrodes (length 1cm

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