SYNTHESIS AND CHARACTERIZATION OF INDIUM(III) COMPLEXES CONTAINING 2 DIFFERENT CHELATE LIGANDS OF THE TYPE [HYDROTRIS(3,5-DIMETHYLPYRAZOLYL)BORATE]IN[LIGAND]X

The reaction of a variety of anionic, chelating ligands with [HB(3,5-Me2pz)3]InCl2.THF or [HB(3,5-Me2PZ)3]-InCl2.H(3,5-Me2pz) leads to the formation of a series of mixed-ligand, six-coordinate indium complexes. Four complexes have been prepared with a second poly(pyrazolyl)borate ligand, [HB(3,5-Me2pz)3]In[ligand]X, where ligand = [H2B(PZ)2]-, [H2B(3,5-Me2PZ)2]-, [HB(pz)3]-, or [B(pz)4]-. The observation of a methyl resonance shifted to high field in all of these complexes is shown by the solid-state structure of six-coordinate [HB(3,5-Me2PZ)3]In[H2B(PZ)2]Cl to arise from the fact that one of the 3-position methyl groups of the [HB(3,5-Me2pz)3]- ligand is located between the aromatic rings of the [H2B(pz)2]-ligand. The reaction of [HB(3,5-Me2pz)3]InCl2.THF with other types of uninegative, bidentate ligands leads to the formation of [HB(3,5-Me2pz)3]In[S2CN(C2H5)2]Cl, [HB(3,5-Me2PZ)3]In(O2CCH3)Cl, [HB(3,5-Me2PZ)3]ln[((H3C)3CC(O))2CH]Cl, and [HB(3,5-Me2PZ)3)In[((CF3)C(O))2CH]Cl. The reaction of [HB(3,5-Me2PZ)3]InCl2.THF with the dianionic ligand [S2C2(CN)2]2- leads to the formation of [HB(3,5-Me2PZ)3]In[S2C2(CN)2].THF, characterized as six-coordinate by X-ray crystallography. The reaction of [HB(3,5-Me2PZ)3]InCl2.H(3,5-Me2pz) and [3,5-ButC6H2O2]2- yields [HB(3,5-Me2PZ)3]In[3,5-But2C6H2O2].H(3,5-Me2pz). Crystal data: [HB(3,5-Me2pz)3]In[H2B(pz)2]Cl, monoclinic, P2(1)/n, a = 12.366(3) angstrom, b = 15.098(2) angstrom, c = 14.762(3) angstrom, beta = 96.47(2)degrees, V = 2738.5(10) angstrom3, Z = 4, T = 297 K, R(F) = 3.41%; [HB(3,5-Me2pz)3]In[S2C2(CN)2].THF, triclinic, P1BAR, a = 10.050(4) angstrom, b = 13.178(8) angstrom, c = 15.882(8) angstrom, alpha = 70.34(1)degrees, beta = 75.21(1)degrees, gamma = 76.40(1)degrees, V = 1889(2) angstrom3, Z = 2, T = 242 K, R(F) = 4.10%.