ACS Publications. Most Trusted. Most Cited. Most Read
Titanium(IV) Complexes with N,N′-Dialkyl-2,3-dihydroxyterephthalamides and 1-Hydroxy-2(1H)-pyridinone as Siderophore and Tunichrome Analogues

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2009, 48, 22, 10769-10779
    ADDITION/CORRECTION. This article has been corrected. View the notice.
    Article

    Titanium(IV) Complexes with N,N′-Dialkyl-2,3-dihydroxyterephthalamides and 1-Hydroxy-2(1H)-pyridinone as Siderophore and Tunichrome Analogues
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107
    *To whom correspondence should be addressed. E-mail: [email protected]
    Other Access OptionsSupporting Information (1)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2009, 48, 22, 10769–10779
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic901177c
    Published October 12, 2009
    Copyright © 2009 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    The aqueous chemistry of Ti(IV) with biological ligands siderophores and tunichromes is modeled by using N,N′-dialkyl-2,3-dihydroxyterephthalamides (alTAMs), analogues of catecholamide-containing biomolecules, and 1-hydroxy-2(1H)-pyridinone (1,2-HOPO), an analogue of hydroxamate-containing biomolecules. Both types of ligands stabilize Ti(IV) with respect to hydrolytic precipitation, and afford tractable complexes. Complexes with the methyl derivative of alTAM, meTAM, are characterized by using mass spectrometry and UV/vis spectroscopy. Complexes with etTAM are characterized by the same techniques as well as X-ray crystallography, cyclic voltammetry, and spectropotentiomeric titration. The ESI mass spectra of these complexes in water show both 1:2 and 1:3 metal/ligand species. The X-ray crystal structure of a 1:2 complex, K2[Ti(etTAM)2(OCH3)2]·2CH3OH (1), is reported. The midpoint potential for reduction of 1 dissolved in solution is −0.98 V. A structure for a 1:3 Ti/etTAM species, Na2[Ti(etTAM)3] demonstrates the coordination and connectivity in that complex. Spectropotentiometric titrations in water reveal three metal-containing species in solution between pH 3 and 10. 1,2-HOPO supports Ti(IV) complexes that are stable and soluble in aqueous solution. The bis-HOPO complex [Ti(1,2-HOPO)2(OCH3)2] (5) was characterized by X-ray crystallography and by mass spectrometry in solution, and the tris-HOPO dimer [(1,2-HOPO)3TiOTi(1,2-HOPO)3] (6) was characterized by X-ray crystallography. Taken together, these experiments explore the characteristics of complexes that may form between siderophores and tunichromes with Ti(IV) in biology and in the environment, and guide efforts toward new, well characterized aqueous Ti(IV) complexes. By revealing the identities and some characteristics of complexes that form under a variety of conditions, these studies further our understanding of the complicated nature of aqueous titanium coordination chemistry.

    Copyright © 2009 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The structure of the potassium tetramer from the X-ray crystal structure of complex 1, intramolecular interaction of the N−H hydrogen and the catecholic oxygen, detailed structure of the 1:3 Ti/etTAM species, ESI-MS of complexes 2, 3, 4, and 5 in solution, cyclic voltammetry of 4, the cif file for the imperfectly resolved X-ray crystal structure of complex 2 and the cif file for the X-ray crystal structure of complexes 1, 5, and 6. This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 18 publications.

    1. Katherine M. Buettner and Ann M. Valentine . Bioinorganic Chemistry of Titanium. Chemical Reviews 2012, 112 (3) , 1863-1881. https://doi.org/10.1021/cr1002886
    2. Peter L. Croot . Rapid Determination of Picomolar Titanium in Seawater with Catalytic Cathodic Stripping Voltammetry. Analytical Chemistry 2011, 83 (16) , 6395-6400. https://doi.org/10.1021/ac201450k
    3. Angus J. Koller, Shefali Saini, Ivis F. Chaple, M. Andrey Joaqui‐Joaqui, Brett M. Paterson, Michelle T. Ma, Philip J. Blower, Valérie C. Pierre, Jerome R. Robinson, Suzanne E. Lapi, Eszter Boros. A General Design Strategy Enabling the Synthesis of Hydrolysis‐Resistant, Water‐Stable Titanium(IV) Complexes. Angewandte Chemie 2022, 134 (22) https://doi.org/10.1002/ange.202201211
    4. Angus J. Koller, Shefali Saini, Ivis F. Chaple, M. Andrey Joaqui‐Joaqui, Brett M. Paterson, Michelle T. Ma, Philip J. Blower, Valérie C. Pierre, Jerome R. Robinson, Suzanne E. Lapi, Eszter Boros. A General Design Strategy Enabling the Synthesis of Hydrolysis‐Resistant, Water‐Stable Titanium(IV) Complexes. Angewandte Chemie International Edition 2022, 61 (22) https://doi.org/10.1002/anie.202201211
    5. L.N. Grant, J.R. Aguilar-Calderón, D.J. Mindiola. Titanium. 2021, 97-161. https://doi.org/10.1016/B978-0-12-409547-2.14923-6
    6. Shweta Sharma, Rohit K. Sharma, Kavita Gaur, José F. Cátala Torres, Sergio A. Loza-Rosas, Anamaris Torres, Manoj Saxena, Mara Julin, Arthur D. Tinoco. Fueling a Hot Debate on the Application of TiO2 Nanoparticles in Sunscreen. Materials 2019, 12 (14) , 2317. https://doi.org/10.3390/ma12142317
    7. Gauthier J.-P. Deblonde, Trevor D. Lohrey, Rebecca J. Abergel. Inducing selectivity and chirality in group IV metal coordination with high-denticity hydroxypyridinones. Dalton Transactions 2019, 48 (23) , 8238-8247. https://doi.org/10.1039/C9DT01031A
    8. Todor Baramov, Bianca Schmid, Ho Ryu, Jinhoon Jeong, Karlijn Keijzer, Leonard von Eckardstein, Mu‐Hyun Baik, Roderich D. Süssmuth. How Many O‐Donor Groups in Enterobactin Does It Take to Bind a Metal Cation?. Chemistry – A European Journal 2019, 25 (28) , 6955-6962. https://doi.org/10.1002/chem.201900453
    9. Ahmed E. Fazary, Yi-Hsu Ju, Ayed S. Al-Shihri, Mohammad Y. Alfaifi, Mohammed A. Alshehri. Biodegradable siderophores: survey on their production, chelating and complexing properties. Reviews in Inorganic Chemistry 2016, 36 (4) https://doi.org/10.1515/revic-2016-0002
    10. David N Bowman, Sriparna Mukherjee, Lyndsay J Barnes, Elena Jakubikova. Linker dependence of interfacial electron transfer rates in Fe(II)-polypyridine sensitized solar cells. Journal of Physics: Condensed Matter 2015, 27 (13) , 134205. https://doi.org/10.1088/0953-8984/27/13/134205
    11. Pawel Jewula, Jean‐Claude Berthet, Jean‐Claude Chambron, Yoann Rousselin, Pierre Thuéry, Michel Meyer. Synthesis and Structural Study of Tetravalent (Zr 4+ , Hf 4+ , Ce 4+ , Th 4+ , U 4+ ) Metal Complexes with Cyclic Hydroxamic Acids. European Journal of Inorganic Chemistry 2015, 2015 (9) , 1529-1541. https://doi.org/10.1002/ejic.201403206
    12. Jiaojiao Gao, Feifei Xing, Yueling Bai, Shourong Zhu. Synthesis, spectroscopy, and binding constants of ketocatechol-containing iminodiacetic acid and its Fe(iii), Cu(ii), and Zn(ii) complexes and reaction of Cu(ii) complex with H2O2 in aqueous solution. Dalton Transactions 2014, 43 (21) , 7964. https://doi.org/10.1039/c4dt00118d
    13. Todor Baramov, Karlijn Keijzer, Elisabeth Irran, Eva Mösker, Mu‐Hyun Baik, Roderich Süssmuth. Synthesis and Structural Characterization of Hexacoordinate Silicon, Germanium, and Titanium Complexes of the E. coli Siderophore Enterobactin. Chemistry – A European Journal 2013, 19 (32) , 10536-10542. https://doi.org/10.1002/chem.201301825
    14. Donna L. Jacob, Joshua D. Borchardt, Leelaruban Navaratnam, Marinus L. Otte, Achintya N. Bezbaruah. UPTAKE AND TRANSLOCATION OF TI FROM NANOPARTICLES IN CROPS AND WETLAND PLANTS. International Journal of Phytoremediation 2013, 15 (2) , 142-153. https://doi.org/10.1080/15226514.2012.683209
    15. Anna Dammshäuser, Peter L. Croot. Low colloidal associations of aluminium and titanium in surface waters of the tropical Atlantic. Geochimica et Cosmochimica Acta 2012, 96 , 304-318. https://doi.org/10.1016/j.gca.2012.07.032
    16. Geert Dehaen, Svetlana V. Eliseeva, Kristof Kimpe, Sophie Laurent, Luce Vander Elst, Robert N. Muller, Wim Dehaen, Koen Binnemans, Tatjana N. Parac‐Vogt. A Self‐Assembled Complex with a Titanium(IV) Catecholate Core as a Potential Bimodal Contrast Agent. Chemistry – A European Journal 2012, 18 (1) , 293-302. https://doi.org/10.1002/chem.201101413
    17. Zhenbo Ma, Brian Moulton. Recent advances of discrete coordination complexes and coordination polymers in drug delivery. Coordination Chemistry Reviews 2011, 255 (15-16) , 1623-1641. https://doi.org/10.1016/j.ccr.2011.01.031
    18. William R. McNamara, Rebecca L. Milot, Hee-eun Song, Robert C. Snoeberger III, Victor S. Batista, Charles A. Schmuttenmaer, Gary W. Brudvig, Robert H. Crabtree. Water-stable, hydroxamate anchors for functionalization of TiO2 surfaces with ultrafast interfacial electron transfer. Energy & Environmental Science 2010, 3 (7) , 917. https://doi.org/10.1039/c001065k
    Download PDF
    Go to Inorganic Chemistry
    Get e-Alerts
    Get e-Alerts

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2009, 48, 22, 10769–10779
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic901177c
    Published October 12, 2009
    Copyright © 2009 American Chemical Society
    Request reuse permissions

    Article Views

    971

    Altmetric

    -

    Citations

    18
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.