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Recrystallization fromtolueneformsacicularcrystals. [6], Titanocene dichloride has being investigated as a potential anticancer drug (currently in clinical trials). TSCATS. Acta Histochem. ; Dias, A.R. Accessibility StatementFor more information contact us atinfo@libretexts.orgor check out our status page at https://status.libretexts.org. Examples: Titanocene dichloride is used to preparetitanocene pentasulfide, a precursor to unusual alloptropes of sulfur: Structure of pentasulfur-The resulting pentasulfur-titanocene complex is allowed to react with polysulfur dichloride to give the desired cyclosulfur of in the series:[10]. Titanocene, TiCp2, is itself so highly reactive that it is not known but it can be trapped by conducting the reduction in the prsence of ligands. for more information. The tumor inhibition influence upon human lung carcinomas xenografted into athymic mice by titanocene dichloride has been studied by Kopf-Maier.56 In the case of lung adenocarcinoma, titanocene dichloride inhibited tumor growth by more than 50% resulting in treated/control values of 20-50%. Transition metal complexes with 18 electrons are also referred to as saturated, and there will be no other empty low-lying orbitals available for extra ligand coordination.
The d electron count is a chemistry formalism used to describe the electron configuration of the valence electrons of a transition metal center in a coordination complex. It is far more common for metal centers to have bonds to other atoms through metallic bonds or covalent bonds. H. Wang, H. Lin, Y. The Cp compound has not been prepared. The Aufbau principle and Madelung's rule would predict for period n that the ns orbitals fill prior to the (n1)d orbitals. [all data], Dillard and Kiser, 1969 Read more about how to correctly acknowledge RSC content. ; Rabinovich, I.B. In this context, the main limitation of this bioinspired approach is, in fact, its extraordinary stereoselectivity, which avoids obtainingcis-fused decalins and/or substituents in axial positions. The more recent ligand field theory offers an easy to understand explanation that models phenomena relatively well. [29] Related reactions occur with diynes. titanocene dichloride, Schwartz's reagent. The following components were used in generating the plot: Additonal code used was developed at NIST: Copyright Clearance Center request page. The 18 electron rule is usually followed in metal complexes with strong field ligands that are good donors and acceptors (for example, CO ligands). Future versions of this site may rely on
Name matches: cp2ticl2 bis (cyclopentadienyl)titanium dichloride. [4], Cp2TiCl2 is a versatile precursor to many Ti(II) derivatives. It exists as a bright red solid that slowly hydrolyzes in air. It is supposed that the apparent virus induction acts as a fortifying factor in the course of tumor inhibition by TDC, and the formation of type-A-virus particles can be recognized. [3]The mechanism by which it acts is not fully understood; however, it has been conjectured that its activity might be attributable to the compounds interactions with the proteintransferrin. Prominent examples are the ring-methylated derivatives (C5H4Me)2TiCl2and (C5Me5)2TiCl2. Go To: Top, Mass spectrum (electron ionization), References Data from NIST Standard Reference Database 69: NIST Chemistry WebBook The National Institute of Standards and Technology (NIST) uses its best efforts to deliver a high quality copy of the Database and to verify that the data contained therein have been selected on the basis of sound . 1991;91(1):25-37. doi: 10.1016/S0065-1281(11)80288-6. Within this context, Rajanbabu and Nugent reported a series of seminal papers about the potential role of Cp2TiCl as a new tool in organic synthesis.1Soon afterwards, Gansuers group published a collection of relevant papers where a substoichiometric version of this protocol was developed.2Those results were especially important in the development of the corresponding asymmetric reactions using chiral titanocene(III) complexes.3After these inspiring works, titanocene(III) complexes, essentially titanocene(III) chloride (Cp2TiCl), have recently emerged as a powerful tool in organic synthesis. [17] The same compound had been reported earlier by a lithium aluminium hydride reduction[18] and sodium amalgam reduction[19] of titanocene dichloride, and studied by 1H NMR[20] prior to its definitive characterisation. Experimentally it has been observed that not only are the ns electrons removed first, even for unionized complexes all of the valence electrons are located in the (n1)d orbitals. Since the (n1)d shell is predicted to have higher energy than the ns shell, it might be expected that electrons would be removed from the (n1)d shell first. }, Subscribe to Drug Approvals International, titanocene dichloride, dichlorobis(cyclopentadienyl)titanium(IV), Except where otherwise noted, data are given for materials in their, Add email in subscribe box and get email of posts, Application in preparing sulfur allotropes. Still, generally, the types of ligands in a complex determine if the complex would follow the 18 electron rule or not. [24] One family of derivatives are the titanocyclopentadienes. * Items in stock locally ship in 1-2 business days. Intracellular localization of titanium within xenografted sensitive human tumors after treatment with the antitumor agent titanocene dichloride. The original synthesis by Wilkinson and Birmingham, using sodium cyclopentadienide,[4] is still commonly used:[5], It can also be prepared by using freshly distilled cyclopentadiene rather than its sodium derivative:[6], Focusing on the geometry of the Ti center, Cp2TiCl2 adopts a distorted tetrahedral geometry (counting Cp as a monodentate ligand). Miessler, G.; Tarr, D. (1998). There are many examples of every possible d electron configuration. If your information is correct and you are still not able to view the requested certificates, Please The Ti-Cl distance is 2.37 and the Cl-Ti-Cl angle is 95. 1271-19-8) in F344/N Rats (Gavage Studies) PMID 12637960; National Toxicology Program technical report series 1991 Sep; 399 (? Long, B. Ni, T. He, S. Zhang, H. Zhu and X. Wang,
Other Sources. Coordination Complexes of Titanium(IV) for Anticancer Therapy. jcamp-dx.js and Depending on the geometry of the final complex, either all three of the np orbitals or portions of them are involved in bonding, similar to the ns orbitals. This metallocene is a common reagent in organometallic and organic synthesis. Thismetalloceneis a common reagent inorganometallicandorganic synthesis. Private communication (see http://webbook.nist.gov/chemistry/om/). Data from NIST Standard Reference Database 69: The National Institute of Standards and Technology (NIST) [all data], Condorelli, Fragala, et al., 1975 Chem. The two orbitals that are involved in bonding form a linear combination with two ligand orbitals with the proper symmetry. available from the NIST/EPA/NIH Mass Spectral Library. This is somewhat analogous to the octet and Lewis structure rules of main group elements in a simplified rationale. It is exists as a bright red solid, forming acicular crystals when crystallized from toluene. *TCI frequently reviews storage conditions to optimize them. The following syntheses demonstrate some of the compounds that can be generated by reduction of titanocene dichloride in the presence of acceptor ligands:[20]. 09/21/2011. Pavarini, E.; Koch, E.; Anders, F. et al., eds (2012). Alkyne and benzyne derivatives of titanocene are well known. on behalf of the United States of America. C10H10I2Ti(solution)+(solution) = 2C10H10ClITi(solution), By formula: C10H10I2Ti(solution)+C10H10Cl2Ti(solution) = 2C10H10ClITi(solution), C30H28Fe2Ti(cr)+2(4.40)(solution) = 2(cr)+(cr), By formula: C30H28Fe2Ti(cr)+2(HCl4.40H2O)(solution) = 2C10H10Fe(cr)+C10H10Cl2Ti(cr), C22H20O2Ti(cr)+2(5.55)(solution) = 2(cr)+(cr), By formula: C22H20O2Ti(cr)+2(HCl5.55H2O)(solution) = 2C6H6O(cr)+C10H10Cl2Ti(cr), C14H10Cl6O4Ti(cr)+2(4.40)(solution) = (cr)+2(cr), By formula: C14H10Cl6O4Ti(cr)+2(HCl4.40H2O)(solution) = C10H10Cl2Ti(cr)+2C2HCl3O2(cr), C10H10N6Ti(cr)+2(4.18)(solution) = (cr)+2(g), By formula: C10H10N6Ti(cr)+2(HCl4.18H2O)(solution) = C10H10Cl2Ti(cr)+2HN3(g), C14H10F6O4Ti(cr)+2(4.40)(solution) = (cr)+2(l), By formula: C14H10F6O4Ti(cr)+2(HCl4.40H2O)(solution) = C10H10Cl2Ti(cr)+2C2HF3O2(l), (cr)+2(5.55)(solution) = (cr)+2(g), By formula: C12H16Ti(cr)+2(HCl5.55H2O)(solution) = C10H10Cl2Ti(cr)+2CH4(g), C11H13ClTi(cr)+(4.40)(solution) = (cr)+(g), By formula: C11H13ClTi(cr)+(HCl4.40H2O)(solution) = C10H10Cl2Ti(cr)+CH4(g), Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Mass spectrum (electron ionization), References, Notes, Data compiled as indicated in comments: PMC This metallocene is a common reagent in organometallic and organic synthesis. d 1 Examples: molybdenum(V) chloride, vanadyl acetylacetonate, vanadocene dichloride, vanadium tetrachloride. [15][16], Reduction with zinc gives the dimer of bis(cyclopentadienyl)titanium(III) chloride in a solvent-mediated chemical equilibrium:[21][22], Cp2TiCl2 is a precursor to TiII derivatives. Chem., 1975, 87, 311. This conversion can be effected with TiCl4or by reaction withSOCl2. It is expected that in near future judicious designs of new titanocene(III) complexes can resolve this drawback. [all data], Tel'noi and Rabinovich, 1977 (C5H4-C5H4)2Fe2 Data compiled by: NIST Mass Spectrometry Data Center, William E. Wallace, director. InChI=1S/2C5H5.2ClH.Ti/c2*1-2-4-5-3-1;;;/h2*1-5H;2*1H;/q;;;;+2/p-2, National Institute of Standards and For example, in the MO diagram provided for the [Ti(H2O)6]3+ the ns orbital which is placed above (n1)d in the representation of atomic orbitals (AOs) is used in a linear combination with the ligand orbitals, forming a very stable bonding orbital with significant ligand character as well as an unoccupied high energy antibonding orbital which is not shown. Titanocene dichloride is the organotitanium compound with the formula (5-C5H5)2TiCl2, commonly abbreviated as Cp2TiCl2. and Informatics, X-ray Photoelectron Spectroscopy Database, version 4.1, NIST Mass Spectrometry Data Center, William E. Wallace, director, Modified by NIST for use in this application. [all data], Cauletti, Clark, et al., 1980 [all data], Dias, Salema, et al., 1981 for more information. Furthermore, titanocene can catalyze C-C bond metathesis to form asymmetric diynes. It is exists as a bright red solid, forming acicular crystals when crystallized from toluene. Instead it is generated in the presence of trapping ligands such as PhCCPh and CO2 to give the 5-membered metallacycles. Relat. [2], Cp2TiCl2 continues to be prepared similarly to its original synthesis by Wilkinson and Birmingham:[3]. [30], Titanocene dichloride was investigated as an anticancer drug. by the U.S. Secretary of Commerce on behalf of the U.S.A. the library and [3][27], Natural product synthesis is an exigent test for newly developed methodologies. Chem Biol Interact. Sorry for the inconvenience. its accompanying search program. Intracellular mapping of the distribution of metals derived from the antitumor metallocenes. Corresponding authors, a Recrystallization fromtolueneformsacicularcrystals conditions to optimize them Cp2TiCl2 is a common reagent in organometallic and synthesis! Kiser, 1969 Read more about how to correctly acknowledge RSC content metathesis to form asymmetric diynes )... ( 11 ) 80288-6, vanadocene dichloride, Schwartz & # x27 ; s reagent generally... Group elements in a simplified rationale information contact us atinfo @ libretexts.orgor out. Bonds to other atoms through metallic bonds or covalent bonds P501: Dispose of contents/ container an... 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Abbreviated as Cp2TiCl2 following components were used in generating the plot: code... Ligand field theory offers an easy to understand explanation that models phenomena relatively well is far more common metal... Red solid, forming acicular crystals when crystallized from toluene a potential anticancer drug, Ni! In near future judicious designs of new titanocene ( III ) Complexes can resolve drawback... To form asymmetric diynes a complex determine if the complex would follow the 18 electron rule or not bonds other... Vanadium tetrachloride best efforts to deliver a high quality copy of the distribution of metals from. On Name matches: Cp2TiCl2 bis ( cyclopentadienyl ) titanium dichloride 24 ] One family of derivatives the! Complexes can resolve this drawback antitumor agent titanocene dichloride, Schwartz & # x27 ; s reagent form. Solid that slowly hydrolyzes in air spectrum display requires a browser with JavaScript and P501: Dispose contents/. 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