Synthesis and characterization of cadmium, copper and zinc complexes with scorpionate ligand hydrotris[3-(p-anisyl)-5-methylpyrazol-1-yl]borate [HB{pz~(An, Me}_3]. X-ray structure of [Cd(OAc)(Hpz~(Me, An)(HB{pz~(An, Me)}_3)]·CH_2Cl_2

摘要

A series of new scorpionate complexes, CdCI(HpzMe.An)(HB{pzAn.Me}_3) (I), (Cd(OAc)(HpzMe.An)(HB{pzAn.Me}_3)fCH_2Cl_2 (2), ZnCI(HB{pzAn.Me}_3) (3), Zn(OAc)(HB{pZAn.Me}_3) (4), Cu(OAc)(HpzMe.An)(HB{pzAn.Me}_3).CH_2Cl_2 (5) and (CuCI(HpzMe.An)(HB{pzAn.Me}_3)fCH_2Cl_2 (6), were prepared by reacting MX_2 (M=Cd~(2+), Zn~(2+), CU~(2+); X=CI-, OAc-) with ligand, K(HB{pZAn.Me}_3J (pZAn.Me = 3-(p-anisyl)-5-methylpyrazolyIJ. The zinc ion in complexes 3 and 4 are four-coordinate, while copper and cadmium is five-coordinated with an additional substituted pyrazole, HpZMe.An, in I, 2, 5 and 6. The infrared bands Va.(CO_2) and V.(CO_2) indicate acetate is an unidentate ligand in 2 and 4, but a bridging one or an intermediate mode between unidentate and bidentate ligand in 5. The 'H NMR spectra of I and 2 show threefold symmetry in solution. The ESR spectra of 5 and 6 in CH_2Cl_2 exhibit a pseudoaxial symmetrical{d_(x2-y2)}~1configuration at copper. The single crystal structure of 2 shows that the coordination environment around Cd~(2 +) is a distorted square pyramidal, with a N atom of tridentate HB{pZAn.Me}_3 apical. The acetate acts as a unidentate ligand, and an intramolecular N-H...O hydrogen bond exists between the uncoordinated oxygen of acetate and the pyrazolic proton.