The complete array of those hydrotris(pyrazolyl/thioimidazolyl)borate ligands that were developed and used in the author's laboratories, with N3, N2S, NS2, and S3 donor sets, was scanned for their ability to form Zn-OH2 and Zn-OH complexes. The coordination motifs found were Zn-OH2, Zn-OH, Zn-OH-Zn, and Zn-O2H3-Zn. Of these, the well-established Zn-OH motif was complemented with novel species bearing N3, NS2, and S3 tripods. The Zn-OH2 motif was observed only with pyrazolylborate ligands and only in unusual situations with coordination numbers higher than 4 for zinc. The new Zn-OH-Zn motif was realized for three different pyrazolylborates, for one NS2 tripod, and for two S3 tripods. Finally, it was verified that the Zn-O2H3-Zn motif again occurs only with pyrazolylborate ligands. The new complexes were identified by a total of 11 structure determinations.
The cover picture shows the Alhambra in Granada, the home town of the Spanish author of this paper. The Moors in their desert dreamt of palaces abundant with water, and that is why they built the Alhambra. Likewise, the water‐soluble encapsulating pyrazolylborate ligand, shown as an (aqua)zinc complex set in one of Alhambra's gardens, is the realization of a long‐standing dream of the Freiburg group, whose biomimetic zinc complex chemistry was previously confined by the hydrophobicity of the model complexes, typically the zinc hydroxide complex shown in the background. The abundance of red (carbonyl oxygen) and green (amide nitrogen) atoms in the foreground complex visualizes its hydrophilicity due to the carboxamide substituents on the tripod ligand. Details are discussed in the article by H. Vahrenkamp et al. on p. 3869 ff.
By refinement of Trofimenko's procedures, four new tris(pyrazolyl)borate (Tp) ligands bearing pyridyl and carboxamide substituents at the 3-positions of the pyrazole rings, were obtained. Two of them were identified by structure determinations of their potassium salts. Their coordinative properties were explored by preparing Tp*Zn-X complexes, with X = Cl, Br, I, NO 3 , OAc, phenolate, thiophenolate and diorganophosphate, including the cationic complexes [Tp*Zn·L] + with L = methanol and pyrazole. From the spectra and structure determinations of these complexes it has become evident
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