NICKEL(II) AND COBALT(II) PHOSPHINOTHIOIC-N-ORGANYLAMIDATO CHELATES [R2P(S)NR']2M - MAGNETIC-PROPERTIES AND CRYSTAL-STRUCTURES

Phosphinothioic-N-organylamidato chelates [R2P(S)NR']2M (R, R' = organyl; M = Ni, Co) 1, 2 have been obtained by reaction of MCl2 with [R2P(S)NR']Li. According to magnetic and spectroscopic measurements (UV/VIS) Ni(II) complexes 1d (R = i-Pr, R' = Me), 1h (R = t-Bu, R' = Me), 1i (R = t-Bu, R' = Et) and 1 m (R = t-Bu, R' = Ph) are planar in solid state. For 1i transgeometry of the donor atoms in the chromophore NiN2S2 has been proved. Ni(II) complexes 1a (R = Me, R' = i-Pr) and 1b (R = Me, R' = c-Hex) show magnetic moments of c. 1.2 B.M. Magnetic moments of all other solid complexes 1, 2 are in a range usually found with tetrahedral coordination. In solution 1c (R = Me, R' = t-Bu), 1e-g (R = i-Pr; R' = i-Pr, c-Hex, t-Bu), and 1j-l (R = t-Bu; R' = i-Pr, c-Hex, t-Bu) are entirely tetrahedral while with 1a, 1b, 1i, and 1m there exists an equilibrium planar half arrow right over half arrow left tetrahedral. This is shifted to the right with increasing R and R' the influence of R being less than that of R'. The crystal structures of 1k (R = t-Bu, R' = c-Hex) and 2a (R, R'= t-Bu) reveal a distorted tetrahedral coordination. 1k: orthorhombic, a = 1343.7(1), b = 1514.9(1), c = 1632.4(2) pm; Pccn, Z = 4, 3205 reflections, R = 0.03. 2a: orthorhombic, a = 1637.9(2), b = 2 997.0(3), c = 1282.4(1) pm; Pbca, Z = 8, 4742 reflections, R = 0.04.