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1

Gansäuer, Andreas, Andreas Okkel, Lukas Schwach, Laura Wagner, Anja Selig, and Aram Prokop. "Triazol-substituted titanocenes by strain-driven 1,3-dipolar cycloadditions." Beilstein Journal of Organic Chemistry 10 (July 17, 2014): 1630–37. http://dx.doi.org/10.3762/bjoc.10.169.

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An operationally simple, convenient, and mild strategy for the synthesis of triazole-substituted titanocenes via strain-driven 1,3-dipolar cycloadditions between azide-functionalized titanocenes and cyclooctyne has been developed. It features the first synthesis of titanocenes containing azide groups. These compounds constitute ‘second-generation’ functionalized titanocene building blocks for further synthetic elaboration. Our synthesis is modular and large numbers of the complexes can in principle be prepared in short periods of time. Some of the triazole-substituted titanocenes display high
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2

Hogan, Megan, James Claffey, Eoin Fitzpatrick, Thomas Hickey, Clara Pampillón, and Matthias Tacke. "Synthesis and Cytotoxicity Studies of Titanocene C Analogues." Metal-Based Drugs 2008 (September 30, 2008): 1–7. http://dx.doi.org/10.1155/2008/754358.

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From the carbolithiation of 6-N,N-dimethylamino fulvene (3) and 2,4[bis(N,N-dimethylamino)methyl]-N-methylpyrrolyl lithium (2a), N-(N′,N′-dimethylaminomethyl)benzimidazolyl lithium (2b)' or p-(N,N-dimethylamino)methylphenyl lithium (2c), the corresponding lithium cyclopentadienide intermediate (4a–c) was formed. These three lithiated intermediates underwent a transmetallation reaction with TiCl4' resulting in N,N-dimethylamino-functionalised titanocenes 5a–c. When these titanocenes were tested against a pig kidney epithelial cell line (LLC-PK), the IC50 values obtained were of 23, and 52 μM fo
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3

Selig, Anja, Laura Wagner, Iris Winkler, Thorsten Lauterbach, Andreas Gansaeuer, and Aram Prokop. "Carbonyl-Substituted Titanocenes as New Cytostatic Agents Against Lymphoma and Leukemia in Childhood." Blood 110, no. 11 (2007): 4208. http://dx.doi.org/10.1182/blood.v110.11.4208.4208.

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Abstract Acute lymphoblastic leukemia (ALL) is the most common malignant disease in childhood. Despite a relatively good prognosis approximately one fourth of the patients suffers from relapse and, consequently, a worse prognosis. Only 40% of these children with relapsed ALL will survive. Patients who fail to achieve a complete remission in chemotherapy do not survive. This explains the need for new compounds that may overcome resistance against clinically employed cytostatic drugs. In the present study we examined novel titan-containing agents concerning their cytotoxic potential with great s
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4

Deally, Anthony, Frauke Hackenberg, Grainne Lally, and Matthias Tacke. "Synthesis and Biological Evaluation of Achiral Indole-Substituted Titanocene Dichloride Derivatives." International Journal of Medicinal Chemistry 2012 (June 12, 2012): 1–13. http://dx.doi.org/10.1155/2012/905981.

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Six new titanocene compounds have been isolated and characterised. These compounds were synthesised from their fulvene precursors using Super Hydride (LiBEt3H) followed by transmetallation with titanium tetrachloride to yield the corresponding titanocene dichloride derivatives. These complexes are bis-[((1-methyl-3-diethylaminomethyl)indol-2-yl)methylcyclopentadienyl] titanium (IV) dichloride (5a), bis-[((5-methoxy-1-methyl,3-diethylaminomethyl)indol-2-yl)methylcyclopentadienyl] titanium (IV) dichloride (5b), bis-[((1-methyl,3-diethylaminomethyl)indol-4-yl)methylcyclopentadienyl] titanium (IV)
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5

Horáček, Michal, Jan Merna, Róbert Gyepes, Jan Sýkora, Jiří Kubišta, and Jiří Pinkas. "Titanocene and ansa-titanocene complexes bearing 2,6-bis(isopropyl)phenoxide ligand(s). Syntheses, characterization and use in catalytic dehydrocoupling polymerization of phenylsilane." Collection of Czechoslovak Chemical Communications 76, no. 1 (2011): 75–94. http://dx.doi.org/10.1135/cccc2010133.

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Aryloxychloro and bis(aryloxy) titanocenes of general formula L2TiCl2–x(OAr′)x where L = η5-C5H5 (x = 1 (1) and 2 (2)), L2 = SiMe2(η5-C5H4)2 (x = 1 (3) and 2 (4)), and Ar′ = 2,6-(CHMe2)2C6H3 were prepared by the reaction of corresponding titanocene dichloride with LiOAr′ and characterized by spectroscopic methods and compound 3 by single crystal X-ray diffraction analysis. The bulky aryloxy ligand in 1 and 3 exerts a hindered rotation around the Ti–O bond on the 1H NMR time scale, resulting in its dynamic behavior in CDCl3 solution. Variable temperature NMR measurements proved the rotation bar
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6

Vassylyev, O., A. Panarello, and J. Khinast. "Enantioselective Hydrogenations with Chiral Titanocenes." Molecules 10, no. 6 (2005): 587–619. http://dx.doi.org/10.3390/10060587.

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7

Gansäuer, Andreas, Iris Winkler, Dennis Worgull, et al. "Modular Synthesis of Functional Titanocenes." Organometallics 27, no. 21 (2008): 5699–707. http://dx.doi.org/10.1021/om800700c.

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8

Yan, Qing, Ken Tsutsumi, and Kotohiro Nomura. "Synthesis and structural analysis of aryloxo-modified trinuclear half-titanocenes, and their use as catalyst precursors for ethylene polymerisation." RSC Advances 7, no. 66 (2017): 41345–58. http://dx.doi.org/10.1039/c7ra07581b.

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The synthesis and structural analysis of aryloxo-modified trinuclear half-titanocenes have been explored: the Cp* analogues showed higher activities for ethylene polymerisation than the related mononuclear analogues.
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9

Skoupilova, Hana, Roman Hrstka, and Martin Bartosik. "Titanocenes as Anticancer Agents: Recent Insights." Medicinal Chemistry 13, no. 4 (2017): 334–44. http://dx.doi.org/10.2174/1573406412666161228113650.

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10

Olszewski, Ulrike, and Gerhard Hamilton. "Mechanisms of Cytotoxicity of Anticancer Titanocenes." Anti-Cancer Agents in Medicinal Chemistry 10, no. 4 (2010): 302–11. http://dx.doi.org/10.2174/187152010791162261.

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11

Cangönül, Asli, Maike Behlendorf, Andreas Gansäuer, and Maurice van Gastel. "Radical-Based Epoxide Opening by Titanocenes." Inorganic Chemistry 52, no. 20 (2013): 11859–66. http://dx.doi.org/10.1021/ic401403a.

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12

Ikai, Shigeru, Jun Yamashita, Yoshiyuki Kai, et al. "Butadiene polymerization with various half-titanocenes." Journal of Molecular Catalysis A: Chemical 140, no. 2 (1999): 115–19. http://dx.doi.org/10.1016/s1381-1169(98)00227-1.

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13

Dalas, E., N. Klouras, and C. Maniatis. "Inhibition of hydroxyapatite formation by titanocenes." Langmuir 8, no. 3 (1992): 1003–6. http://dx.doi.org/10.1021/la00039a043.

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14

Pampillón, Clara, Oscar Mendoza, Nigel J. Sweeney, Katja Strohfeldt, and Matthias Tacke. "Diarylmethyl substituted titanocenes: Promising anti-cancer drugs." Polyhedron 25, no. 10 (2006): 2101–8. http://dx.doi.org/10.1016/j.poly.2006.01.007.

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15

Undheim, Kjell, and Vidar Bjørnstad. "Stereoselective Syntheses of Spirane Bridged Semi-titanocenes." Synthesis 2008, no. 6 (2008): 962–70. http://dx.doi.org/10.1055/s-2008-1032205.

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16

Gao, Li Ming, José L. Vera, Jaime Matta, and Enrique Meléndez. "Synthesis and cytotoxicity studies of steroid-functionalized titanocenes as potential anticancer drugs: sex steroids as potential vectors for titanocenes." JBIC Journal of Biological Inorganic Chemistry 15, no. 6 (2010): 851–59. http://dx.doi.org/10.1007/s00775-010-0649-7.

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17

Lukešová, Lenka, Michal Horáček, Petr Štěpnička, et al. "Synthesis and crystal structures of thermally stable titanocenes." Journal of Organometallic Chemistry 663, no. 1-2 (2002): 134–44. http://dx.doi.org/10.1016/s0022-328x(02)01726-6.

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18

Liu, Jianfei, Haiyan Ma, Jiling Huang, Yanlong Qian, and Albert S. C. Chan. "Syndiotactic polymerization of styrene with half-sandwich titanocenes." European Polymer Journal 35, no. 3 (1999): 543–45. http://dx.doi.org/10.1016/s0014-3057(98)00137-2.

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19

Gansäuer, Andreas, Dieter Franke, Thorsten Lauterbach, and Martin Nieger. "A Modular and Efficient Synthesis of Functional Titanocenes." Journal of the American Chemical Society 127, no. 33 (2005): 11622–23. http://dx.doi.org/10.1021/ja054185r.

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20

Zhang, Yong-Qiang, Verena Jakoby, Katharina Stainer, et al. "Amide-Substituted Titanocenes in Hydrogen-Atom Transfer Catalysis." Angewandte Chemie International Edition 55, no. 4 (2015): 1523–26. http://dx.doi.org/10.1002/anie.201509548.

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21

Zhang, Zhenhua, Tobias Hilche, Daniel Slak, et al. "Titanocenes as Photoredox Catalysts Using Green‐Light Irradiation." Angewandte Chemie International Edition 59, no. 24 (2020): 9355–59. http://dx.doi.org/10.1002/anie.202001508.

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22

Koutsopoulos, S., E. Dalas, and N. Klouras. "Inhibition of Hydroxyapatite Crystal Growth by Substituted Titanocenes." Langmuir 16, no. 16 (2000): 6745–49. http://dx.doi.org/10.1021/la000070j.

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23

Wang, Yue, Y. Q. Liang, Y. J. Liu, and J. Z. Liu. "Carbonyl adducts of open titanocenes — syntheses and structures." Journal of Organometallic Chemistry 443, no. 2 (1993): 185–89. http://dx.doi.org/10.1016/0022-328x(93)80296-n.

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24

Lima dos Santos, Hugo Felix, Daniel de L. Pontes, and Caio L. Firme. "Relation between topology and stability of bent titanocenes." Journal of Molecular Modeling 19, no. 8 (2013): 2955–64. http://dx.doi.org/10.1007/s00894-013-1817-9.

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25

Sweeney, Nigel, William M. Gallagher, Helge Müller-Bunz, Clara Pampillón, Katja Strohfeldt, and Matthias Tacke. "Heteroaryl substituted titanocenes as potential anti-cancer drugs." Journal of Inorganic Biochemistry 100, no. 9 (2006): 1479–86. http://dx.doi.org/10.1016/j.jinorgbio.2006.04.006.

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26

Zhang, Zhenhua, Tobias Hilche, Daniel Slak, et al. "Titanocenes as Photoredox Catalysts Using Green‐Light Irradiation." Angewandte Chemie 132, no. 24 (2020): 9441–45. http://dx.doi.org/10.1002/ange.202001508.

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27

Claffey, James, Megan Hogan, Helge Müller-Bunz, Clara Pampillón, and Matthias Tacke. "Synthesis and cytotoxicity studies of methoxy benzyl substituted titanocenes." Journal of Organometallic Chemistry 693, no. 3 (2008): 526–36. http://dx.doi.org/10.1016/j.jorganchem.2007.11.037.

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28

Zirngast, Michaela, Ulrich Flörke, Judith Baumgartner, and Christoph Marschner. "Oligosilylated group 4 titanocenes in the oxidation state +3." Chemical Communications, no. 37 (2009): 5538. http://dx.doi.org/10.1039/b910637e.

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29

Lukešová, Lenka, Michal Horáček, Petr Štěpnička, et al. "Irregular cyclization reactions in titanocenes bearing pendant double bonds." Journal of Organometallic Chemistry 689, no. 11 (2004): 1919–29. http://dx.doi.org/10.1016/j.jorganchem.2004.02.040.

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30

Méndez, Luis Miguel Menéndez, Anthony Deally, Donal F. O'Shea, and Matthias Tacke. "Synthesis and cytotoxicity studies of achiral azaindole-substituted titanocenes." Heteroatom Chemistry 22, no. 2 (2011): 148–57. http://dx.doi.org/10.1002/hc.20668.

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31

Nie, Yujing, Junquan Sun, Jin Cheng, Hua Ren, and Herbert Schumann. "Ethylene polymerization by diphenyl ether bridged dinuclear titanocenes/MAO." Journal of Applied Polymer Science 108, no. 6 (2008): 3702–6. http://dx.doi.org/10.1002/app.27775.

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32

Gao, Li, Wilson Maldonado, Xiomara Narváez-Pita, José Carmona-Negrón, Jesus Olivero-Verbel, and Enrique Meléndez. "Steroid-Functionalized Titanocenes: Docking Studies with Estrogen Receptor Alpha." Inorganics 4, no. 4 (2016): 38. http://dx.doi.org/10.3390/inorganics4040038.

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33

Sutton, Scott C., Michael H. Nantz, and Sean R. Parkin. "Synthesis of ansa-titanocenes via a double-Skattebol rearrangement." Organometallics 12, no. 6 (1993): 2248–57. http://dx.doi.org/10.1021/om00030a040.

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34

Pinkas, Jiří, Ivana Císařová, Róbert Gyepes, Jiří Kubišta, Karel Mach, and Michal Horáček. "Substituent effects in reduction-induced synthesis of ansa-titanocenes." Transition Metal Chemistry 41, no. 2 (2015): 143–52. http://dx.doi.org/10.1007/s11243-015-0006-3.

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35

Firme, Caio L., Daniel de L. Pontes, and Octávio A. C. Antunes. "Topological study of bis(cyclopentadienyl) titanium and bent titanocenes." Chemical Physics Letters 499, no. 4-6 (2010): 193–98. http://dx.doi.org/10.1016/j.cplett.2010.09.038.

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36

Weber, Holger, James Claffey, Megan Hogan, Clara Pampillón, and Matthias Tacke. "Analyses of Titanocenes in the spheroid-based cellular angiogenesis assay." Toxicology in Vitro 22, no. 2 (2008): 531–34. http://dx.doi.org/10.1016/j.tiv.2007.09.014.

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37

Deally, Anthony, James Claffey, Brendan Gleeson, et al. "Synthesis and preliminary cytotoxicity studies of achiral pyrrolyl-substituted titanocenes." Polyhedron 29, no. 12 (2010): 2445–53. http://dx.doi.org/10.1016/j.poly.2010.05.018.

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38

Noh, Seok Kyun, Sanghyun Kim, Youngdo Yang, Won Seok Lyoo, and Dong-ho Lee. "Preparation of syndiotactic polystyrene using the doubly bridged dinuclear titanocenes." European Polymer Journal 40, no. 2 (2004): 227–35. http://dx.doi.org/10.1016/j.eurpolymj.2003.10.010.

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39

Deally, Anthony, Brendan Gleeson, Helge Müller-Bunz, Siddappa Patil, Donal F. O’Shea, and Matthias Tacke. "Novel achiral indole-substituted titanocenes: Synthesis and preliminary cytotoxicity studies." Journal of Organometallic Chemistry 696, no. 5 (2011): 1072–83. http://dx.doi.org/10.1016/j.jorganchem.2010.10.039.

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40

Fletcher, Andrew E. D., Jonathan D. Hyatt, Kang Min Ok, and Dermot O'Hare. "Catalytic dechlorination of polychlorinated biphenyls (PCBs) using amine functionalised titanocenes." Green Chemistry 11, no. 9 (2009): 1343. http://dx.doi.org/10.1039/b906311k.

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41

Wilson, Anne M., Thomas E. Waldman, Arnold L. Rheingold, and Richard D. Ernst. "Ring fusion and polycyclic ring constructions via half-open titanocenes." Journal of the American Chemical Society 114, no. 15 (1992): 6252–54. http://dx.doi.org/10.1021/ja00041a057.

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42

Kaleta, Katharina, Alexander Hildebrandt, Frank Strehler, et al. "Ferrocenyl-Substituted Metallacycles of Titanocenes: Oligocyclopentadienyl Complexes with Promising Properties." Angewandte Chemie International Edition 50, no. 47 (2011): 11248–52. http://dx.doi.org/10.1002/anie.201105248.

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43

Thanh, Nguyen Thi Le, Seok Kyun Noh, Won Seok Lyoo, and Dong-Ho Lee. "POLYMERIZATION OF ISOBUTYL VINYL ETHER CATALYSED BY DINUCLEAR HALF-TITANOCENES." Chinese Journal of Polymer Science 26, no. 05 (2008): 611. http://dx.doi.org/10.1142/s0256767908003345.

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44

Hogan, Megan, Brendan Gleeson, and Matthias Tacke. "Synthesis and Preliminary Cytotoxicity Studies of Achiral Indolyl-Substituted Titanocenes." Organometallics 29, no. 4 (2010): 1032–40. http://dx.doi.org/10.1021/om901031m.

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45

Gansäuer, Andreas. "Titanocenes as Electron Transfer Catalysts: Reagent Controlled Catalytic Radical Reactions." Synlett 1998, no. 8 (1998): 801–9. http://dx.doi.org/10.1055/s-1998-1785.

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46

Stojković, Olivera, and Walter Kaminsky. "Syndiospecific Polymerization of Styrene with Aryl Substituted Indenyl Halfsandwich Titanocenes." Macromolecular Chemistry and Physics 205, no. 3 (2004): 357–62. http://dx.doi.org/10.1002/macp.200300170.

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47

Gao, Li Ming, and Enrique Meléndez. "Cytotoxic Properties of Titanocenyl Amides on Breast Cancer Cell Line MCF-7." Metal-Based Drugs 2010 (May 4, 2010): 1–6. http://dx.doi.org/10.1155/2010/286298.

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A new titanocenyl amide containing flavone as pendant group has been synthesized by reaction of titanocenyl carboxylic acid chloride and 7-Aminoflavone and structurally characterized by spectroscopic methods. This species and eight previously synthesized titanocenyl amide complexes have been tested in breast adenocarcinoma cancer cell line, MCF-7. The functionalization of titanocene dichloride with amides enhances the cytotoxic activity in MCF-7. Two sets of titanocenyl amides can be identified, with IC50<100 μM and IC50>100 μM. The most cytotoxic species is Cp(CpCO-NH-C6H4-(CH2)2CH3)TiC
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48

Sala, Giorgio Della, Alessandra Lattanzi, Tania Severino, and Arrigo Scettri. "The first application of titanocenes in the asymmetric oxidation of sulfides." Journal of Molecular Catalysis A: Chemical 170, no. 1-2 (2001): 219–24. http://dx.doi.org/10.1016/s1381-1169(01)00072-3.

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49

Machat, Martin R., Christian Jandl, and Bernhard Rieger. "Titanocenes in Olefin Polymerization: Sustainable Catalyst System or an Extinct Species?" Organometallics 36, no. 7 (2017): 1408–18. http://dx.doi.org/10.1021/acs.organomet.7b00112.

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50

Strohfeldt, Katja, Helge Müller-Bunz, Clara Pampillón, Nigel J. Sweeney, and Matthias Tacke. "Glycol Methyl Ether and Glycol Amine Substituted Titanocenes as Antitumor Agents." European Journal of Inorganic Chemistry 2006, no. 22 (2006): 4621–28. http://dx.doi.org/10.1002/ejic.200600586.

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