Inorg Chem
Institut Für Chemie, Carl von Ossietzky Universität Oldenburg, D-26111 Oldenburg, Federal Republic of Germany.
Published: February 2024
The reaction of hydrazones with bis(π-η:σ-η-pentafulvene)titanium complexes leads to both hydrazonido and hydrazido complexes depending on the interaction of the hydrazone with the fulvene ligand of the metal complex. The molecular structures mostly reveal κ, side-on coordination of the hydrazonido ligand due to the deprotonation of the N-H bond by one of the fulvene moieties. Instead of deprotonation, the reaction of the bis(adamantylidene fulvene)titanium complexes with cinnamon aldehyde phenylhydrazone leads to κ coordination. By using donating groups in the backbone of the hydrazone ligands, there are exceptions to this coordination mode due to the insertion of the C═N double bond into the Ti-C bond of the pentafulvene moiety. Using 2-pyridinecarboxaldehyde phenylhydrazone, a formal κ,, ligand system is formed by the coordination of the pyridine nitrogen atom to the metal center via consecutive N-H deprotonation and insertion. Finally, the use of salicylaldehyde phenylhydrazone ultimately produces a complex with the κ,, coordination mode by double deprotonation of the hydrazone N-H and O-H functions. Because of its slow conversion to the final product, the intermediate was isolated as an insertion product with consecutive O-H deprotonation, showing a κ, coordination mode of the hydrazido ligand.
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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10865377 | PMC |
http://dx.doi.org/10.1021/acs.inorgchem.3c04301 | DOI Listing |
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