Routes to new hafnium(IV) tetraaryl porphyrins and crystal structures of unusual phosphate-, sulfate-, and peroxide-bridged dimers

Alexander Falber, Louis Todaro, Israel Goldberg*, Michael V. Favilla, Charles Michael Drain

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

New routes for the synthesis of mono tetraaryl porphyrinato hafnium(IV) complexes, Hf(IV)Por(L)2, are reported, where the secondary ligands, L, are determined by the method of purification. These synthetic routes cater to the solubility of the macrocycles and provide access to Hf(IV) complexes of meso tetraaryl porphyrins bearing diverse functional groups such as phenyl, tolyl, pyridyl, pentafluorophenyl, and carboxyphenyl. The latter three derivatives significantly expand the repertoire of hafnium porphyrinates. One route refluxes the porphyrin with HfCl4 in 1-chloronaphthalene or in a mixed solvent of 1-chloronaphthalene and o-cresol. A second, solventless method is also reported wherein the porphyrin is mixed with Hf(cp) 2Cl2 and heated to give the metalated porphyrin in good yields. Simultaneous purification and formation of stable porphyrinato hafnium(IV) diacetate complexes, Hf(Por)OAc2, is accomplished by elution over silica gel using 3-5% acetic acid in the eluent. Exchange of the acetate ligands for other oxo-bearing ligands can be nearly quantitative, such as p-aminobenzoate (PABA), pentanoate (pent), or octanoate (oct). Notably, we find that two to three of a variety of small multitopic dianions such as peroxo (O2-2), SO4-2, and HPO 4-2 serve to bridge between two Hf(Por) moieties to form stable dimers. The crystal structures of this library of Hf(Por) complexes are reported, and we note that careful analysis of crystallography data reveals (Por)Hf(μ-η2-O2)2Hf(Por) rather than four bridging oxo or hydroxy ions.

Original languageEnglish
Pages (from-to)454-467
Number of pages14
JournalInorganic Chemistry
Volume47
Issue number2
DOIs
StatePublished - 21 Jan 2008

Funding

FundersFunder number
National Institute of General Medical SciencesS06GM060654
National Center for Research ResourcesG12RR003037

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