1271-29-0Relevant academic research and scientific papers
The reaction of titanocene bis(ferrocenylacetylide) and bis(ruthenocenylacetylide) with silver cation: Formation of bis(Ti-tweezers) silver complexes
Hayashi, Yukiko,Osawa, Masahisa,Kobayashi, Kimiko,Sato, Takuma,Sato, Masaru,Wakatsuki, Yasuo
, p. 169 - 175 (1998)
Titanocene bis(acetylide) where the acetylide has ferrocenyl or ruthenocenyl terminal group (C5H4R)2Ti{(CC)n-Mc}2, reacted with 0.5 equivalent amount of AgPF6 giving cationic heptanuclear c
Homogeneous catalytic dehydrocoupling/dehydrogenation of amine-borane adducts by early transition metal, group 4 metallocene complexes
Sloan, Matthew E.,Staubitz, Anne,Clark, Timothy J.,Russell, Christopher A.,Lloyd-Jones, Guy C.,Manners, Ian
, p. 3831 - 3841 (2010)
The efficient catalytic dehydrocoupling of a range of amine-borane adducts, R'RNH·BH3 (R' = R = Me 1a; R' = R = Pr 1b; R' = Me, R = CH2Ph 1c) by a series of group 4 metallocene type precatalysts has been demonstrated. A reduction in catalytic activity was detected upon descending the group and also on substitution of the cyclopentadienyl (Cp) ligands with sterically bulky or electron-donating substituents. Precatalysts Cp2TiCl2/2nBuLi and Cp2Ti(PMe 3)2, which are believed to act as precursors to [Cp 2Ti], were found to promote the transformation of 1a to [Me 2N-BH2l2 (3a) in a homogeneous catalytic process. Mechanistic studies identified the linear dimer Me2NH- BH2-NMe2-BH3 (2a) as a reaction intermediate, which subsequently undergoes further catalytic dehydrogenation to form cyclic dimer 3a. Synthesis of the 2H-isotopologues of 1a allowed the extraction of phenomenological kinetic isotope effects for 1a → 2a and 2a → 3a from initial rate data, which permitted the proposal of a catalytic cycle with plausible intermediates. Support for the presence of an active Ti(II) catalyst was provided by the lack of reactivity of Ti(III) complexes TiCl 3 and Cp2TiCl or Ti(O) in the form of THF soluble colloids or bulk Ti powder toward 1a or 1b. Modeling of the rates of consumption of 1a and formation of 3a during catalysis by Cp2Ti(PMe3) 2 supported this conclusion and allowed the proposal of a two cycle, four step reaction mechanism. The proposed first cycle generates 2a in a two step process. In the second cycle, interaction of 2a with the same catalyst then results in a catalytic dehydrogenative ring closing reaction to form 3a, also in a two step process.
Synthesis and characterization of Cp2Ti-containing organometallics via in situ oxidative-addition of 'Cp2Ti' intermediate
Song, Li-Cheng,Liu, Peng-Chong,Han, Cong,Hu, Qing-Mei
, p. 119 - 125 (2002)
A simple and convenient route for synthesizing Cp2 Ti-containing compounds (RS)2TiCp2 (1, R = 1-C10H7; 2, R = CH2=CHCH2; 3, R = n-C5H11; 4, R = CH2CO 2Me; 5, R = CH2CO2Et; 6, R = (η5-C5H5)Fe(η5 -C5H4CH2)) and [η2-OC(Ph) =C(Ph)O] TiCp2 (7) has been developed. This route starts from Cp2TiCl2 and involves an in situ oxidative-addition of the intermediate 'titanocene' with corresponding RSSR and benzil. While 7 was previously prepared by another route, 1-6 and one starting material [(η5-C5H5) Fe(η5-C5H4CH2)] 2S2 (8) are new and have been characterized by elemental analysis, IR and 1H-NMR spectroscopy, as well as by X-ray diffraction analysis for 1, 6 and 7. Furthermore, the electrochemical properties of 1-6 have been studied by cyclic voltammetry.
Paramagnetic Titanium(III) and Zirconium(III) Metallocene complexes as precatalysts for the dehydrocoupling/dehydrogenation of Amine-Boranes
Helten, Holger,Dutta, Barnali,Vance, James R.,Sloan, Matthew E.,Haddow, Mairi F.,Sproules, Stephen,Collison, David,Whittell, George R.,Guy C. Lloyd-Jones,Manners, Ian
, (2013)
Complexes of Group 4 metallocenes in the +3 oxidation state and amidoborane or phosphidoborane function as efficient precatalysts for the dehydrocoupling/dehydrogenation of amine-boranes, such as Me 2NH·BH3 (see scheme). Such Ti
FORMATION REACTIVITIES, AND MOLECULAR STRUCTURES OF PHOSPHINE DERIVATIVES OF TITANOCENE - ISOLATION AND CHARACTERIZATION OF A TITANIUM MONOOLEFIN pi COMPLEX.
Edwards,Rogers,Sikora,Atwood,Rausch
, p. 416 - 426 (2007/10/02)
The synthesis of several new phosphine derivatives of titanocene under both thermally and photochemically induced conditions are described. The molecular structures of two of these complexes have been elucidated by means of single-crystal X-ray diffraction methods, and the bonding modes of the respective phosphine ligands to titanium are compared. Finally, the utility of the triethylphosphine analogue as a versatile intermediate for the generation of pi -acetylenic and pi -monoolefinic complexes of titanium is reported. Refs.
