Synthesis and Reactivity of Four- and Five-Coordinate Low-Spin Cobalt(II) PCP Pincer Complexes and Some Nickel(II) Analogues

[Image: see text] Anhydrous CoCl(2) or [NiCl(2)(DME)] reacts with the ligand PCP(Me)-iPr (1) in the presence of nBuLi to afford the 15e and 16e square planar complexes [Co(PCP(Me)-iPr)Cl] (2) and [Ni(PCP(Me)-iPr)Cl] (3), respectively. Complex 2 is a paramagnetic d(7) low-spin complex, which is a useful precursor for a series of Co(I), Co(II), and Co(III) PCP complexes. Complex 2 reacts readily with CO and pyridine to afford the five-coordinate square-pyramidal 17e complexes [Co(PCP(Me)-iPr)(CO)Cl] (4) and [Co(PCP(Me)-iPr)(py)Cl] (5), respectively, while in the presence of Ag(+) and CO the cationic complex [Co(PCP(Me)-iPr)(CO)(2)](+) (6) is afforded. The effective magnetic moments μ(eff) of all Co(II) complexes were derived from the temperature dependence of the inverse molar magnetic susceptibility by SQUID measurements and are in the range 1.9 to 2.4 μ(B). This is consistent with a d(7) low-spin configuration with some degree of spin–orbit coupling. Oxidation of 2 with CuCl(2) affords the paramagnetic Co(III) PCP complex [Co(PCP(Me)-iPr)Cl(2)] (7), while the synthesis of the diamagnetic Co(I) complex [Co(PCP(Me)-iPr)(CO)(2)] (8) was achieved by stirring 2 in toluene with KC(8) in the presence of CO. Finally, the cationic 16e Ni(II) PCP complex [Ni(PCP(Me)-iPr)(CO)](+) (10) was obtained by reacting complex 3 with 1 equiv of AgSbF(6) in the presence of CO. The reactivity of CO addition to Co(I), Co(II), and Ni(II) PCP square planar complexes of the type [M(PCP(Me)-iPr)(CO)](n) (n = +1, 0) was investigated by DFT calculations, showing that formation of the Co species, 6 and 8, is thermodynamically favorable, while Ni(II) maintains the 16e configuration since CO addition is unfavorable in this case. X-ray structures of most complexes are provided and discussed. A structural feature of interest is that the apical CO ligand in 4 deviates significantly from linearity, with a Co–C–O angle of 170.0(1)°. The DFT-calculated value is 172°, clearly showing that this is not a packing but an electronic effect.