ABSTRACT
As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, Ph3P, Ph2P-(CH2)2-PPh2 (dppe), Ph3As, Et3N, PhNH2, C5H5N, CH3CN, Ph2CHCN)) in the presence of a wide range of Lewis acids (Ti(IV), Hf(IV), Zr(IV), Al, Cu(I), Zn, Mn(II), Co(II) halides and iodine), a number of substituted derivatives of the octahydrotriborate anion [B3H7Nu] are obtained. It is found that the use of TiCl4, AlCl3, ZrCl4, HfCl4, CuCl and iodine leads to the highest product yields. In this case, it is most likely that the reaction proceeds through the formation of an intermediate [B3H7-HMXnx], which was detected by NMR spectroscopy. The structures of [Ph3P·B3H7] and [PhNH2·B3H7] were determined by X-ray diffraction.
ABSTRACT
The interaction of hafnium(IV) salts (oxide-dichloride, chloride, and bromide) with nitrilotriacetic acid (NTA), diethylenetriamminepentaacetic acid (DTPA), 1,2-diaminocyclohexanetetraacetic acid (CDTA), 1,3-dipropylmino-2-hydroxy N,N,N',N'-tetraacetic acid (dpta), and N-(2-hydroxyethyl)ethylenediamine triacetic acid (HEDTA) has been studied. The corresponding complexes Na2[Hf(NTA)2]·3H2O (1), Na[HfDTPA]·3H2O (2), [HfCDTA(H2O)2] (3), and Na[Hf2(dpta)2]·7.5H2O·0.5C2H5OH (4) have been isolated and characterized and their structures have been determined by single crystal X-ray diffraction. Biological studies of [HfCDTA(H2O)2] have shown that in 5% glucose solution this complex has low toxicity and good contrasting ability.
ABSTRACT
Interaction of [Cu2B10H10] with 2,2'-bipyridine (bipy) afforded a novel binuclear discrete complex of the [Cu2(bipy)2B10H10] composition. Two copper(I) atoms coordinate a bridge boron cage through an apical edge and a triangular BBB face situated at its opposite apical vertices to form four 3c2e (CuHB) and one 2c2e Cu-B bonds. The charge density model was obtained by density functional theory calculations of isolated molecule and crystal. The resultant densities were analyzed using the quantum theory of atoms in molecules (QTAIM) and electron localizability indicator (ELI-D). The geometry and the topological parameters of copper(I) coordination environment were found to be sensitive to crystal-field effect. An annulus of flat electron density ρ(r) and small ∇(2)ρ(r) is formed at dianion faces. As a result, some of the expected B-B, Cu-B, or Cu-H bond critical points are absent. The topological instability in the region of multicentered bonds is observed. The Cu-B bonding was found to be presumably electrostatic in nature, which could be the reason of topological isomerism for copper(I) decaborates. The results show that an unambiguous real-space criterion for multicentered bonding between transition metals and polyhedral boron anions is not yet given. The molecular graph for this class of compounds does not provide a definitive picture of the chemical boding and can be complemented with other descriptors, such as virial graphs and the ELI-D distribution.
