Synthesis and solution stability of water-soluble κ2N,κO-bis(3,5-dimethylpyrazolyl)ethanol manganese(i) tricarbonyl bromide (CORM-ONN1)

Ralf Mede; Juliane Traber; Moritz Klein; Helmar Görls; Guido Gessner; Patrick Hoffmann; Michael Schmitt; Jürgen Popp; Stefan H Heinemann; Ute Neugebauer; Matthias Westerhausen

doi:10.1039/c6dt03551e

Synthesis and solution stability of water-soluble κ²N,κO-bis(3,5-dimethylpyrazolyl)ethanol manganese(i) tricarbonyl bromide (CORM-ONN1)

Dalton Trans. 2017 Jan 31;46(5):1684-1693. doi: 10.1039/c6dt03551e.

Authors

Affiliations

¹ Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University (FSU), Humboldstraße 8, D-07743 Jena, Germany. m.we@uni-jena.de.
² Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, D-07743 Jena, Germany and Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Straße 9, D-07745 Jena, Germany.
³ Center for Molecular Biomedicine (CMB), Department of Biophysics, Friedrich Schiller University Jena and Jena University Hospital, Hans-Knöll-Straße 2, D-07745 Jena, Germany.
⁴ Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Straße 9, D-07745 Jena, Germany and Center for Sepsis Control and Care (CSCC), Jena University Hospital, Am Klinikum 1, D-07747 Jena, Germany.
⁵ Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, D-07743 Jena, Germany and Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Straße 9, D-07745 Jena, Germany and Center for Sepsis Control and Care (CSCC), Jena University Hospital, Am Klinikum 1, D-07747 Jena, Germany.

PMID: 28102423
DOI: 10.1039/c6dt03551e

Abstract

The reaction of (OC)₅MnBr with bis(3,5-dimethyl-1-pyrazolyl)methane yields [{(Pz^Me2)₂CH₂}Mn(CO)₃Br] (1). The use of tridentate heteroscorpionates such as bis(3,5-dimethyl-1-pyrazolyl)acetic acid and 2,2-bis(3,5-dimethyl-1-pyrazolyl)ethanol leads to the formation of mononuclear [(OC)₃Mn{(Pz^Me2)₂CH-CO₂}] (2) and [(OC)₃Mn{(Pz^Me2)₂CH-CH₂OH}]Br (3, CORM-ONN1). Salt-like photoCORM 3 is soluble in aqueous media up to a concentration of 200 μM, non-toxic up to an approx. 65 μM solution and releases all carbonyl ligands upon irradiation. The molecular complexes 1 and 2 are insoluble in aqueous solutions. CORM-ONN1 (3) slowly degrades in methanol yielding iCORM 4, consisting of the complex cation [{(Pz^Me2)₂CH-CH₂OH}{(Pz^Me2)₂CH-CH₂O}Mn]⁺ and the [Mn(CO)₅]^- counter anion with the cations linked to a dimeric unit by intermolecular hydrogen bridges between the alcohol and alkoxide functionalities.