Di-tert-butyl thiopyridazine boratrane complexes of Co, Ni and Cu

Add time:08/08/2019    Source:sciencedirect.com

The thiopyridazine based scorpionate ligand sodium tris(3,5-di-tert-butyl-6-thioxopyridazin-1(6H)-yl)hydroborate (NaTntBu,tBu) with two tert-butyl substituents in ortho- and para-position of the thio group was synthesized and fully characterized. Corresponding metallaboratrane complexes [M{B(PntBu,tBu)3}Cl] (M = Co, Ni, Cu) as well as [M{B(PnMe,tBu)3}Cl] (M = Co, Ni) were prepared in good yields. All complexes were characterized by spectroscopic means as well as by single crystal X-ray diffraction studies exhibiting short metal boron bonds (between 2.0186(17) Å and 2.069(3) Å) compared to previously reported boratranes. The two tert-butyl groups attached to the heterocycle significantly increases the solubility of NaTntBu,tBu and the derived metal complexes in apolar solvents compared to the system bearing the smaller substituents. The higher steric demand of the tert-butyl versus methyl group enhances the distortion from trigonal bipyramidal towards square pyramidal which effects the electronic situation within the complexes evidenced by the elongated metal chlorine bond trans to boron.

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