Magneto-Structural Correlation of Five-Coordinate Trigonal Bipyramidal High Spin Cobalt(II) Complexes.

Here, we combined magnetometry, multi-frequency electronic paramagnetic resonance, and wave function based ab initio calculations to investigate magnetic properties of two high spin Co(II) complexes Co(BDP R P) (BDP R P=2,6-bis((2-(S)-di(4-R)phenylhydroxylmethyl-1-pyrrolidi-nyl)methyl)pyridine, R=H for 8; R= t Bu for 9). Complexes 8 and 9 featuring effective D 3h symmetry were found to possess D=24.0 and 32.0 cm -1 , respectively, in their S=3/2 ground states of 1 e ' ' d x z / y z 4 1 e ' d x y / x 2 - y 2 2 1 a 1 ' d z 2 1 ${{\left(1{{\rm e}}^{{\rm { {^\prime}}}{\rm { {^\prime}}}}\right({d}_{xz/yz}\left)\right)}^{4}{\left(1{{\rm e}}^{{\rm { {^\prime}}}}\right({d}_{{xy/{x}^{2}-y}^{2}}\left)\right)}^{2}{\left(1{{\rm a}}_{1}^{{\rm { {^\prime}}}}\right({d}_{{z}^{2}}\left)\right)}^{1}}$ . Ligand field analyses revealed that the low-lying d-d excited states make either positive or vanishing contributions to D. Hence, total positive D values were measured for 8 and 9, as well as related D 3h high spin Co(II) complexes. In contrast, negative D values are usually observed for C 3v congeners. In-depth analyses suggested that lowering symmetry from D 3h to C 3v induces orbital mixing between 1 e d x z / y z ${1{\rm e}\left({d}_{xz/yz}\right)}$ and 2 e d x y / x 2 - y 2 ${2{\rm e}\left({d}_{{xy/{x}^{2}-y}^{2}}\right)}$ and admixes excited state 4 A 2 1 e → 2 e ${{}^{4}{{\rm A}}_{2}\left(1e\to 2e\right)}$ into the ground state. Both factors turn the total D value progressively negative with the increasing distance (δ) of the Co(II) center out of the equatorial plane. Therefore, δ determines the sign and magnitude of final D values of five-coordinate trigonal bipyramidal S=3/2 Co(II) complexes as measured for a series of such species with varying δ.