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.
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
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.
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.
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.
