COMPLEXES OF COBALT(II) CHLORIDE WITH THE TRIPODAL TRISPHOSPHANE TRIPHOS - SOLUTION DYNAMICS, SPIN-CROSSOVER, REACTIVITY, AND REDOX ACTIVITY

Depending on the reaction conditions, different products are obtained from the reaction of CoCl2 with CH3C(CH2PPh2)(3) (triphos), including the law-spin complexes [(triphos)Co(mu-Cl)(2)Co(triphos)](2+) (1(2+)) and [(triphos)CoCl2] (3), their solid-state structures being determine d by X-ray methods. In solution, additionally, a four-coordinate high- spin complex [(eta(2)-triphos)CoCl2] (2) is present, its concentration relative to that of 3 depending on the solvent and the temperature. T he reactivity of these species toward Lewis acids is investigated lead ing to the novel heterodinuclear complexes [(triphos)Co(mu-Cl)(2)MCl2] (M = Fe (5), Co (6)). Reactions with Lewis bases L yield complexes of the rare type [(triphos)CoCl(L)](+) (L = CO (7(+)), PMe3 (8(+)), NH3 (9(+)), CH3CN (10(+))). One electron reduction of 3 leads to the previ ously prepared pseudotetrahedral [(triphos)(CoCl)-Cl-I] complex 11, an d one-electron oxidation to the novel trigonal-bipyramidal low-spin co mplex [(triphos)(CoCl2)-Cl-III](+) (12(+)).