POCKET SEMIQUINONATE COMPLEXES OF COBALT(II), COPPER(II), AND ZINC(II) PREPARED WITH THE HYDROTRIS(CUMENYLMETHYLPYRAZOLYL)BORATE LIGAND

摘要

3,5-Di-tert-butyl-1,2-semiquinonate (3,5-DBSQ) complexes of Co(II), Cu(II), and Zn(II) have been prepared that contain the hydrotris(cumenylmethyl-pyrazolyl)borate (Tp(Cum,Me)) coligand. Tp(Cum,Me)M(OH), M=Cu and Zn with 3,5-di-tert-butylcatechol. Tp Co-Cum,Co-Me(3,5-DBSQ) was prepared by a reaction between (Tp(Cum,Me))(2)Co and 3,5-DBCat. The identity of (Tp(Cum,Me))(2)Co in this reaction was confirmed by a structure determination [(Tp(Cum,Me))(2)Co: orthorhombic, Pbcn, a=17.7189(4) Angstrom, b=17.8406(3) Angstrom, c=25.7123(6) Angstrom, V=7964.1(3) Angstrom(3), Z=4, R(F)=0.054]. Intersecting cumenyl substituents of the pyrazolylborate ligand encapsulate the Co(II) ion. Structural characterization on all three members of the Tp(Cum,Me)M(3,5-DBSQ) series has been carried out. The complexes of Co(II) and Zn(II) are isomorphous and isostructural [Tp(Cum,Me)Co(3,5-DBSQ): triclinic, P (1) over bar, a=14.4631(2) Angstrom, b=18.5438(3) Angstrom, c=21.6142(2) Angstrom, alpha=79.8430(10)degrees, beta=90.0900(10)degrees, gamma=84.9900(10)degrees, V=5683.45(13) Angstrom(3), Z=4, R(F)=0.072; Tp(Cum,Me)Zn(3,5-DBSQ), triclinic, P (1) over bar, a=14261(3) Angstrom, b=18.760(7) Angstrom, c=21.710-(4) Angstrom, alpha =80.049(12)degrees,