309-89-7Relevant articles and documents
The first early transition metal perfluorovinyl complexes: The synthesis of Cp2M(CF=CF2)nX2-n (Cp: Η5-C5H5-; M=Ti, Zr; X=Cl or F) and structures of Cp2Ti(CF=CF2)nX2-n (X=Cl, F) via Ti K-edge EXAFS studies
Banger, Kulbinder K.,Brisdon, Alan K.
, p. 301 - 309 (1999)
A new route to perfluorovinyl compounds, recently reported by us, has been used to prepare the first examples of early transition metal complexes of the type Cp2M(CF=CF2)nXn-2 (Cp: η5-C5H5-; M=Ti, Zr; X=Cl or F). These compounds are obtained in high yield from the two-stage, one-pot, reaction of HFC-134a (CF3CH2F) with two equivalents of BuLi, followed by addition of Cp2MX2 (M=Ti, Zr, X=F, Cl). For two of the titanium-containing compounds Ti K-edge EXAFS data have been recorded from which distances for the titanium-carbon bond of the perfluorovinyl group of 2.033(12) and 2.050(18) A in Cp2Ti(CF=CF2)2 and Cp2Ti(CF=CF2)F are obtained. This is the first report of structural data for any perfluorovinyl organometallic compound, and the distances obtained are consistent with the perfluorovinyl group binding in a simple sigma fashion.
Organometallic transition metal derivatives containing fluorine. V. Some perfluoro-1-methylpropenyl derivatives of metal carbonyls and metal cyclopentadienyls
King,Zipperer
, p. 2119 - 2125 (1972)
Reactions of various transition metal halide derivatives with perfluoro-1-methylpropenylsilver, C4F7Ag, in dichloromethane solution at room temperature give the corresponding perfluoro-1-methylpropenyl transition metal derivatives. T
Preparation of Ti(IV), Zr(IV) and Sn(IV) metal alkyls containing the (PriO)3SiCH2 fragment
Cauzzi, Daniele,Graiff, Claudia,Marazzi, Marianna,Predieri, Giovanni,Tiripicchio, Antonio
, p. 256 - 262 (2002)
By reaction of RMgCl (R = (PriO)3SiCH2) with Cp2TiCl2, Cp2ZrCl2 and SnCl4, the stable metal alkyls Cp2TiClR (1), Cp2TiR2, Cp2/su
New fluoride derivative of a dinuclear titanium (III) fulvalene complex: Crystal structure of [(η5-C5H5)Ti(μ-F)] 2(μ-η5:η5-C10H 8)
Yu, Peihua,Murphy, Eamonn F.,Roesky, Herbert W.,Lubini, Paolo,Schmidt, Hans-Georg,Noltemeyer, Mathias
, p. 313 - 316 (1997)
Reduction of titanocene difluoride (Cp2TiF2) with 1.5 equiv of potassium in toluene at 60-100°C affords the dinuclear η5:η5-fulvalene complex [(η5-C5H5)Ti(μ-F)] 2(μ-η5:η5-C10H 8) (2). 2 was also obtained via reaction of Me3SnF with the corresponding chloride and hydride compounds [(η5-C5H5)Ti(μ-X)] 2(μ-η5:η5-C10H 8) (X = Cl, H). 2 has been characterized by mass spectrometry, IR spectroscopy, and chemical analyses. The molecular structure of 2, as determined by the X-ray crystal structural analyses, reveals a Ti2F2 fragment symmetrically folded along the Ti-Ti direction and assuming a butterfly configuration with a dihedral angle of 27.6(2)°. A dihedral angle of 15.3(3)° is observed between the two C5H4 rings of the folded fulvalene ligand.
Organosulfur derivatives of the metal carbonyls. XIII. Some trifluoromethylthio derivatives of metal carbonyls and cyclopentadienyls
King,Welcman
, p. 2540 - 2543 (1969)
Reaction of Mn(CO)5Br with CF3SAg in CH2Cl2 solution gives yellow crystalline [CF3SMn(CO)4]2. However, reaction of Re(CO)5Br with CF3SAg under similar conditions gives not only white [CF3SRe(CO)4]2 but also white CF3SRe(CO)5; the latter compound is converted to [CF3SRe(CO)4]2 upon boiling in cyclohexane. Reaction of C5H5Fe(CO)2I with CF3SAg in acetone solution gives red-brown liquid CF3SFe(CO)2C5H5. Reaction of the π-allyl derivative C3H5Fe(CO)3I with CF3SAg in CH2Cl2 solution gives red liquid CF3SFe(CO)3C3H5. Reaction of C5H5Cr(NO)2Cl with CF3SAg in acetone solution gives yellow-brown crystalline CF3SCr(NO)2C5H5. Reaction of (C5H5)2TiCl2 with CF3SAg does not give a CF3S-Ti derivative. Instead a novel shift of fluorine from carbon to titanium occurs resulting in the formation of yellow (C5H5)2TiF2. The infrared, nmr, and mass spectra of the new compounds are discussed.
Monomeric triorganotin(IV) fluorides containing a C,N-chelating ligand
Bares, Josef,Novak, Petr,Nadvornik, Milan,Jambor, Roman,Lebl, Tomas,Cisarova, Ivana,Ruzicka, Ales,Holecek, Jaroslav
, p. 2967 - 2971 (2004)
The set of four triorganotin(IV) fluorides of general formula {2-[(CH 3)2NCH2]C6H4}R 2SnF, where R is Me (5), n-Bu (6), t-Bu (7), and Ph (8), respectively, has been prepared and characterized using NMR and ESI-MS techniques. The structures of crystalline compounds 5 and 8 were determined using X-ray methods. All compounds are monomeric both in solution using different solvents and in the solid state. The tin central atom is five-coordinated with all carbon atoms in equatorial positions and fluorine and nitrogen, from the intramolecularly coordinated dimethylamino group, in the axial positions of the distorted trigonal bipyramid. The ability of compounds 6 and 8 to perform fluorination of organometallic chlorides was tested on titanocene dichloride. A quantitative yield of Cp2TiF2 was obtained.
Trimethyltin fluoride: A new fluorinating reagent for the preparation of organometallic fluorides
Herzog, Axel,Liu, Feng-Quan,Roesky, Herbert W.,Demsar, Alojz,Keller, Klaus,Noltemeyer, Mathias,Pauer, Frank
, p. 1251 - 1256 (1994)
Me3SnF (1) reacts with Cp′MCl3 to give Cp′MF3 (2, Cp′ = C5Me5, M = Ti; 2a, Cp′ = C5Me4Et, M = Ti; 2b, Cp′ = C5H5, M = Ti; 2c, Cp′ = C5H4Me, M = Ti; 3, Cp′ = C5Me5, M = Zr; 4, Cp′ = C5Me5, M = Hf) in high yields. The reaction of Cp2TiCl2, [C5H3(Me)(SiMe3)]2ZrCl2, and (C5Me5)2HfCl2 with Me3SnF yields Cp2TiF2 (5), [C5H3(Me)(SiMe3)]2ZrF2 (6), and (C5Me5)2HfF2 (7), respectively. Treatment of (Cp*TiClO)3 (Cp* = C5Me5) with Me3SnF leads to the eight-membered ring (Cp*TiFO)4 (8). The reaction of the organotitanium(III) chlorides (Cp2TiCl)2 (Cp = C5H5), [(C5H4Me)2TiCl]2, and Cp*2TiCl with Me3SnF gives the corresponding fluorides (Cp2TiF)2 (9), [(C5H4Me)2TiF]2 (10), and Cp2*TiF (11), respectively. An alternative method for the preparation of compounds 9 and 10 is the reduction of Cp2TiF2 and (C5H4Me)2TiF2, respectively, using sodium amalgam. The structures of 2c, 3, 4, and 10 were determined by single-crystal X-ray diffraction. Compounds 3 and 4 are isostructural and form tetramers in the solid as well as in solution. 10 is a fluorine-bridged dimer in the crystalline state.
EIN ORGANOTITANKOMPLEX MIT ZWEI KOORDINATIV GEBUNDENEN WASSERMOLEKUELEN: (ClO4)2*3C4H8O
Thewalt, Ulf,Klein, Heinz-Peter
, p. 297 - 308 (1980)
(?-C5H5)2Ti(ClO4)2 and H2O react in tetrahydrofuran to form the diaquo complex (ClO4)2*3C4H8O.X-ray analysis shows the titanium atom to be nearly tetrahedrally coordinated.Mean values of distances: Ti-O 2.01 Angstroem, Ti-Z 2.03 Angstroem (Z=center of ring); angles: O-Ti-O 90.4o, Z-Ti-Z 133.3o.The complex crystallizes in the monoclinic space group P21/c with Z=4 and lattice parameters at -100 deg C a 15.324(5), b 10.848(5), c 18.325(5) Angstroem, and β 110.75(3)o.
Palladium-Catalyzed Reductive Coupling Reaction of Terminal Alkynes with Aryl Iodides Utilizing Hafnocene Difluoride as a Hafnium Hydride Precursor Leading to trans-Alkenes
Takahashi, Keita,Ogiwara, Yohei,Sakai, Norio
supporting information, p. 809 - 814 (2018/03/13)
Herein, we describe a reductive cross-coupling of alkynes and aryl iodides by using a novel catalytic system composed of a catalytic amount of palladium dichloride and a promoter precursor, hafnocene difluoride (Cp2HfF2, Cp=cyclopentadienyl anion), in the presence of a mild reducing reagent, a hydrosilane, leading to a one-pot preparation of trans-alkenes. In this process, a series of coupling reactions efficiently proceeds through the following three steps: (i) an initial formation of hafnocene hydride from hafnocene difluoride and the hydrosilane, (ii) a subsequent hydrohafnation toward alkynes, and (iii) a final transmetalation of the alkenyl hafnium species to a palladium complex. This reductive coupling could be chemoselectively applied to the preparation of trans-alkenes with various functional groups, such as an alkyl group, a halogen, an ester, a nitro group, a heterocycle, a boronic ester, and an internal alkyne.
Process for the synthesis of prostaglandin derivatives
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Page/Page column 17, (2010/11/24)
An alternative method for the synthesis of prostaglandin F analogues, in particular, analogues of PGF2α and specifically for the synthesis of latano-prost, wherein the transformation of the lactone intermediate (5) into the corresponding lactol (7) is carried out by treating the lactone intermediate (5) with a silane, preferably polymethylhydrosiloxane (PMHS), in the presence of a titanocene - and preferably titanocene fluoride. The method enables considerable production economies with respect to the conventional reduction of lactone with diisobutylaluminum hydride (DIBAL-H).
