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Potassium tris(3,5-dimethyl-1-pyrazolyl)borate

Potassium tris(3,5-dimethyl-1-pyrazolyl)borate, abbreviated KTp*, is the potassium salt of the anion HB((CH<sub>3</sub>)<sub>2</sub>C<sub>3</sub>N<sub>2</sub>H)<sub>3</sub>. Tp*<sup>−</sup> is a tripodal ligand that binds to a metal in a facial manner, more specifically a Scorpionate ligand. KTp* is a white crystalline solid that is soluble in polar solvents, including water and several alcohols.

Synthesis

KTp* is synthesized in a manner similar to that of KTp by the reaction of potassium borohydride and 3,5-dimethylpyrazole. Hydrogen gas is evolved as each of the pyrazole reacts at the boron. The rate of B-N bond formation becomes more difficult with each successive 3,5-dimethylpyrazolyl due to the increase in steric hindrance around the boron:

3 Me<sub>2</sub>C<sub>3</sub>N<sub>2</sub>H<sub>2</sub> + KBH<sub>4</sub> → KHB(Me<sub>2</sub>C<sub>3</sub>N<sub>2</sub>H)<sub>3</sub> + 3 H<sub>2</sub>

The required dimethylpyrazole is obtained by condensation of hydrazine and acetylacetone.

Role as ligand

The active binding sites in Tp*<sup>−</sup> are the three nitrogen centers that are not bonded to the boron. Although more weakly binding than cyclopentadienyl ligands, Tp*<sup>−</sup> is still a tightly coordinating. The benefit of Tp*<sup>−</sup> over its sister compound Tp<sup>−</sup> is the addition of the methyl groups on the pyrazolyl rings, which increases the steric hindrance of the ligand enough that only one Tp*<sup>−</sup> can bind to a metal. This leaves the remaining coordination sites available for catalysis.

References