Reaktionen von Pentaphenylcyclopentadienylnickel-Komplexen mit Thiuramen und Dithiocarbamat: Nickel in den Oxidationsstufen I, II and III

Add time:08/31/2019    Source:sciencedirect.com

Tetramethylthiuram monosulfide and tetramethylthiuram disulfide react with [(C5Ph5)Ni(NCCH3)2]BF4 (2) to give the black pentaphenylcyclopentadienyl nickel complex [(C5Ph5)Ni{S2CN(CH3)2}]BF4 (7). Its crystal structure has been determined. It is the first 17-electron cyclopentadienyl nickel(III) compound to be structurally characterized. The formation reaction corresponds formally to an oxidative addition of tetramethylthiuram monosulfide and tetramethylthiuram disulfide to the nickel(II) complex 2. The solid-state magnetic moment of the paramagnetic nickel(III) complex 7 is μeff = 1,77 B.M. The reaction of sodium dimethyldithiocarbamate with [(C4Ph5)Ni(CO)Br] yields the dark-red pentaphenylcyclopentadienyl nickel(II) complex [(C5Ph5)Ni{S2CN(CH3)}] (6). Cyclic voltammetry reveals that the dithiocarbamate complex 6 can be oxidised electrochemically and chemically reversibly at +0.265 V vs. SCE to give the cation 7. The reduction at −1.43 V leads to the nickel(I) complex [(C5Ph5Ni{S2CN(CH3)2}]−. The nickel(III) complex 7 can also be prepared on a preparative scale by oxidation of 6 with ferrocene(1 + )tetrafluoroborate in dichloromethane. The reduction of 7 to give 6 is possible in dichloromethane with tetrakis(dimethylamino)ethylene as the reducing agent.

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