A Lacunar Cyclidene Complex of Cobalt II

l2-Dimethyl-3,1 l-bis(l inelhoxyethylidene)-l, 5,9,13-tetraaza-cyelohexadeca-1,4,9,12-tetraene-K yV nickel(Il)] Hexailuorophosphate, 

The starting diacetylated nickel(II) complex I (24 g, 0.102 mol) is dissolved in400mL of dry dichloromethane (distilled from CaH2) in a 1-L one-necked round-bottomed flask equipped with a stirring bar. To this red solution is added 30 g (0.052 mol) of methyl trifluoromethanesulfonate. 

A calcium chloride drying tube is inserted into the ground glass joint of the flask, and the solution is stirred at room temperature for 16 h (overnight is convenient), during which time the color of the reaction mixture changes from deep red to a very dark olive green. 

Product III is a square planar diamagnetic complex, which is readily soluble in acetonitrile or acetone, but less so in methanol or ethanol. Its IR spectrum (KBr pellet) shows a strong characteristic absorption at 3390cm associated with the N—H stretching vibration, and a rich pattern in the double bond region (1640-1570cm ). The presence of triethylamine hydrochloride impurity can be assessed by the presence of bands in the 2400-2800-cm region of the spectrum. The CNMR (CDjCN) S 170.0, 168.3, 159.9, 112.4, 56.2, 51.5, 31.8, 30.6, 30.2, 20.9, and 15.5 relative to TMS. The peaks at 5 170.0, 112.4, 31.8, and 15.5 are broad as a result of rotation about the C—N bond. 

The mixture is cooled to room temperature and filtered. The solvent is removed by rotary evaporation under reduced pressure to give a viscous dark red-brown oily residue. This residue is redissolved in the minimum amount of acetonitrile, and the solution. Filtered if necessary, is applied to a 

---