Small Molecule Chemistry of the Pyrazolylborate−Zinc Unit TpCum,MeZn

M Ruf, H Vahrenkamp - Inorganic chemistry, 1996 - ACS Publications
M Ruf, H Vahrenkamp
Inorganic chemistry, 1996ACS Publications
The synthesis of the highly encapsulating pyrazolylborate ligand hydrotris (3-p-cumenyl-5-
methylpyrazolyl) borate (L= TpCum, Me) and of its zinc hydroxide complex L⊙ Zn− OH (1)
are described. 1 is converted by H2S into the hydrosulfide complex L⊙ Zn− SH (2). Both 1
and 2 seem to be contaminated with traces of the isomeric species 1 'and 2 'containing L
'with one 3-methyl-5-p-cumenyl substituent. Thermal condensations of 1 'and 2 yield the
molecular zinc oxide and sulfide complexes L '⊙ Zn− O− Zn⊙ L '(3 ') and L⊙ Zn− S− Zn⊙ L …
The synthesis of the highly encapsulating pyrazolylborate ligand hydrotris(3-p-cumenyl-5-methylpyrazolyl)borate (L = TpCum,Me) and of its zinc hydroxide complex L·Zn−OH (1) are described. 1 is converted by H2S into the hydrosulfide complex L·Zn−SH (2). Both 1 and 2 seem to be contaminated with traces of the isomeric species 1‘ and 2‘ containing L‘ with one 3-methyl-5-p-cumenyl substituent. Thermal condensations of 1‘ and 2 yield the molecular zinc oxide and sulfide complexes L‘·Zn−O−Zn·L‘ (3‘) and L·Zn−S−Zn·L (4). The hydroxide complex 1 has been found to react readily with cumulated double-bonded species:  CO2 is incorporated in alcoholic solutions to form the alkylcarbonate complexes L·Zn−OCOOR (5). Similarly, CS2 in ethanol forms the O-ethyl dithiocarbonate complex L·Zn−SC(S)OEt (6). SO2 is converted to a bridging sulfito ligand in L·Zn−O-SO−O−Zn·L (7), and phenyl isothiocyanate is bound as a thiocarbamidato ligand in L·Zn−SC(O)NHPh (8). Complexes 1, 2, 2‘, 3‘, 4, 5, and 6 have been confirmed by structure determinations and complexes 7 and 8 by spectral data.
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