Abstract

The knowledge of the properties of pyrazolylborates has been considerably improved both in the solid state and in solution. The hydrates of the sodium and the potassium salts of tetrakis(l-pyrazolyl)borate crystallize in the space group C2/ c, both salts being isomorphous. Regular pyrazole rings conform with a pseudosymmetry plane around a distorted tetrahedral boron atom. Chains along the b axis of two different octahedra of coordination, sharing water oxygens, are linked by H bonds. In solution, a careful 1H, 13C, 11B and 15N NMR study was carried out. The applicability of the rules used to assign H(3) versus H(5) and C(3) vcrsus C(5) in the case of pyrazolylborates was reevaluated. Only for tetrakis(1- pyrazolyl)borate were couplings observed with 1B in 1H, 3C and 5N resonances. The regularity of the properties of bis-, tris- and tetrakispyrazolylborates, allows the calculation of the spectral parameters of the still unknown tris-hydrido(1-pyrazolyl)borate, pzBH 3 −. Finally, the electronic properties, as measured by σ p, of the substituents BH 3 −, pzBH 2 −, pz 2BH − and pz 3B − were estimated.

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