11136-36-0Relevant articles and documents
IR studies at elevated gas pressures. III. Kinetics of the CO induced disproportionation of (C5(CH3)5)2TiX (X=Cl, Br, I)
Luinstra, Gerrit A.,Teuben, Jan H.,Brintzinger, Hans-Herbert
, p. 183 - 190 (1989)
The disproportionation of Cp*2TiClCO (Cp*=μ5-C5(CH3)5) (formed from Cp*2TiCl and CO in toluene solution) into Cp*2TiCl2 and Cp*2Ti(CO)2 has been studied at CO pressures of between 2 and 90
Titanocene - 1,4,6-tris(trimethylsilyl)hex-3-ene-1,5-diyne-3-yl complexes - Crystal structures and their retro reaction
Horá?ek, Michal,Císa?ová, Ivana,Kubi?ta, Ji?í,Spannenberg, Anke,Dallmann, Kai,Rosenthal, Uwe,Mach, Karel
, p. 4592 - 4600 (2004)
The formation of the π-coordinated 1,4,6-tris(trimethylsilyl)hex-3-ene- 1,5-diyne-3-yl ligand at the (TiIII) atom is a general reaction for highly methyl-substituted titanocenes. The retroreaction to 1,4- bis(trimethylsilyl)buta-1,3-diyne is induced by oxidation with PbCl2. Paramagnetic titanocene complexes containing the unsaturated carbyl group which consists of one and half molecule of 1,4-bis(trimethylsilyl)buta-1,3-diyne (BSD) are formed by the reduction of titanocene dichlorides with one molar equivalent of magnesium in the presence of 1.5 molar equivalent BSD in tetrahydrofuran (THF) for titanocene moieties Ti(η5-C 5H5 - nMen)2 (n = 5 (1), 4 (2), and 3 (3)) and Ti{Me2Si(η5-C5Me 4)2} (4). The non-methylated titanocene moiety affords under identical conditions known diamagnetic bis(η5- cyclopentadienyl)-2,4-bis(trimethylsilylethynyl)-3,5-bis(trimethylsilyl) titanacyclopenta-2,4-diene (5) as the major product. Crystal structures of 3 and 4 show the same bonding scheme for the 1,4,6-tris(trimethylsilyl)hex-3-ene-1,5- diyne-3-yl ligand as previously found for compound 1 [P.-M. Pellny, F.G. Kirchbauer, V.V. Burlakov, A. Spannenberg, K. Mach, U. Rosenthal, Chem. Commun. (1999) 2505]. Compound 1 is stable against weak proton donors like methanol or alk-1-ynes even at 90°C, however, it undergoes retroreaction when oxidized by PbCl2 in THF, yielding nearly quantitatively BSD and [TiCl 2(η5-C5Me5)2].
Mono- and dilithiation of [(η7-C7H 7)Ti(η5-C5Me5)] (Pentamethyltroticene) for the synthesis of troticenyl monophosphanes and [2]troticenophanes with C-P and C-Si Bridges
Tagne Kuate, Alain C.,Mohapatra, Swagat K.,Daniliuc, Constantin G.,Jones, Peter G.,Tamm, Matthias
, p. 8544 - 8555 (2012)
Pentamethyltroticene, [(η7-C7H 7)Ti(η5-C5Me5)] (1), can be selectively metalated at the C7H7 ring or at both the C5Me5 and C7H7 rings using pmdta/nBuLi or pmdta/tBuLi mixtures (pmdta = N,N′,N′,N″, N″-pentamethyldiethylenetriamine) in 1/1 and 1/4 ratios, respectively. The mono- and dilithiated species [(η7-C7H 6Li)Ti(η5-C5Me5)]·pmdta (2) and [(η7-C7H6Li)Ti(η5- C5Me4CH2Li)]·pmdta (3) were isolated in high yield and characterized by NMR spectroscopy and elemental analysis. Compound 2 was used to synthesize the pentamethyltroticenyl monophosphane [(η7-C7H6PPh2) Ti(η5-C5Me5)] (4) by reaction with Ph 2PCl, while 3 was treated with RPCl2 (R = Ph, Mes) or Me2SiCl2 to give the carbaphospha- and carbasila[2]troticenophanes [(η7-C7H 6)Ti(η5-C5Me4CH2)]PR (5, R = Ph; 6, R = Mes) and [(η7-C7H 6)Ti(η5-C5Me4CH 2)]SiMe2 (8). The chiral phosphanes 5 and 6 are the first examples of non-iron metallocenophanes with a phosphorus atom in the bridge. The coordination ability of 4 and 6 toward transition metals was demonstrated by reaction with Mo(CO)6 and [(tht)AuCl] (tht = tetrahydrothiophene) or Me2SAuCl and formation of the bimetallic complexes [{η7-C7H6PPh2·Mo(CO) 5}Ti(η5-C5Me5)] (9), [(η7-C7H6PPh2·AuCl) Ti(η5-C5Me5)] (10), and [(η7-C7H6)Ti(η5-C 5Me4CH2)]PMes·AuCl (11). These compounds were structurally characterized by multinuclear 1H, 13C, 31P, and 29Si NMR spectroscopy, UV/vis spectroscopy, electron ionization mass spectrometry (EI-MS), elemental analysis, and single-crystal X-ray diffraction analysis. The molecular structures of 5, 6 and 8 reveal strained sandwich compounds with tilt angles (α) of 18.5(1)° (5), 19.7(7)° (6), and 13.4(2)° (8). Treatment of 2 with ZnCl 2 afforded the pentamethyltroticenyl zinc chloride [(η7-C7H6ZnCl)Ti(η5-C 5Me5)] (12), which was employed in palladium-catalyzed Negishi C-C cross-coupling reactions with phenyl iodide and iodotroticene to afford phenylpentamethyltroticene [(η7-C7H 6Ph)Ti(η5-C5Me5)] (13) and the [7-5]bitroticene [(η7-C7H6)Ti{μ- η5:η7-(C5H4-C 7H6)}Ti(η5-C5Me5)] (14), which bears a bridging sesquifulvalene ligand. The molecular structures of 13 and 14 in the solid state were also determined by single-crystal X-ray diffraction analysis.
Interaction of carbon dioxide with the bis(trimethylsilyl) acetylene complex of permethyltitanocene: Synthesis and structure of the binuclear carbonate complex of permethyltitanocene (Cp2 Ti) 2CO3
Burlakov,Dolgushin,Yanovsky,Struchkov,Shur,Rosenthal,Thewalt
, p. 241 - 247 (1996)
It has been shown that in the interaction of carbon dioxide with the bis(trimethylsilyl)acetylene complex of permethyltitanocene Cp2* Ti(Me3SiC2SiMe3), full displacement of bis(trimethylsilyl)acetylene from the
Reactivity Study of Pyridyl-Substituted 1-Metalla-2,5-diaza-cyclopenta-2,4-dienes of Group 4 Metallocenes
Becker, Lisanne,Rei?, Fabian,Altenburger, Kai,Spannenberg, Anke,Arndt, Perdita,Jiao, Haijun,Rosenthal, Uwe
supporting information, p. 10826 - 10838 (2016/07/27)
In this work the reactivity of 1-metalla-2,5-diaza-cyclopenta-2,4-dienes of group 4 metallocenes, especially of the pyridyl-substituted examples, towards small molecules is investigated. The addition of H2, CO2, Ph?C≡N, 2-py?C≡N, 1,3-dicyanobenzene or 2,6-dicyanopyridine results in exchange reactions, which are accompanied by the elimination of a nitrile. For CO2, a coordination to the five-membered cycle occurs in case of Cp*2Zr(N=C(2-py)?C(2-py)=N). A 1,4-diaza-buta-1,3-diene complex is formed by H-transfer in the conversion of the analogous titanocene compound with CH3?C≡N, PhCH2?C≡N or acetone. For CH3?C≡N a coupling product of three acetonitrile molecules is established additionally. In order to split off the metallocene from the coupled nitriles, we examined reactions with HCl, PhPCl2, PhPSCl2and SOCl2. In the last case, the respective thiadiazole oxides and the metallocene dichlorides were obtained. A subsequent reaction produced thiadiazoles.
Nitrile-nitrile C-C coupling at group 4 metallocenes to form 1-metalla-2,5-diaza-cyclopenta-2,4-dienes: Synthesis and reactivity
Becker, Lisanne,Arndt, Perdita,Jiao, Haijun,Spannenberg, Anke,Rosenthal, Uwe
supporting information, p. 11396 - 11400 (2013/11/06)
The C-C coupling of aryl nitriles at Group 4 metallocenes leads to unusual ring-strained 1-metalla-2,5-diaza-cyclopenta-2,4-dienes. The structural, energetic, and chemical properties of these complexes are described. The reactions of these compounds towar
