625855-35-8

Upstream product

• 1271-66-5 dimethyltitanocene 
• 1665-00-5 dichloromethane-d2 
• 7789-20-0 water-d2 
• 7732-18-5 water 

Downstream Products

• 1388860-58-9 (C(CH₃)3)3PCO₂Ti(C₅H₅)2Cl⁽¹⁺⁾*B(C₆F₅)4^(1-)=(C₄H₉)3PCO₂Ti(C₅H₅)2ClB(C₆F₅)4 

Relevant academic research and scientific papers

The Taming of Redox-Labile Phosphidotitanocene Cations

Tame d0 phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one-electron oxidation of d1 precursors with [Cp2Fe][BPh4]. The electronic structure of these compounds was studied experimentally (EPR, UV/Vis, and NMR spectroscopy, X-ray diffraction analysis) and through DFT calculations. The theoretical analysis of the bonding situation by using the electron localization function (ELF) shows the presence of π-interactions between the phosphido ligand and Ti in the d0 complexes, whereas dπ–pπ repulsion prevents such interactions in the d1 complexes. In addition, CH–π interactions were observed in several complexes, both in solution and in the solid state, between the phosphido ligand and the phosphane arm. The d0 complexes were found to be light sensitive, and decompose through Ti?P bond homolysis to give TiIII species. A naked d0 phosphidotitanocene cation has been trapped by reaction with diphenylacetylene, yielding a Ti/P frustrated Lewis pair (FLP), which was found to be less reactive than a previously reported Zr analog.

Metallocene-catalyzed olefin polymerizations using triphenylcyclopropenium tetrakis(pentafluorophenyl)borate as the activator

Triphenylcyclopropenium (TPCP) tetrakis(pentafluorophenyl)borate activates bis(cyclopentadienyl)dimethyl titanium resulting in a highly reactive initiating system for the polymerization of styrene. In contrast to triphenylmethyl tetrakis(pentafluorophenyl)borate which is quite active in the absence of the metallocene, TPCP borate shows no activity for styrene polymerization in the absence of bis(cyclopentadienyl)dimethyl titanium . TPCP is the most efiicient activator in the carbonium ion - borate class. We propose, based on 1H NMR evidence that reaction of Cp2TiMe 2 and TPCP borate leads to the formation of the cationic Ti complex [Cp2TiMe]+B(C6F5)4 -. Evidence for the latter is also provided by UV-vis spectroscopy in that we found a bathochromic shift of the Cp2TiMe2 LMCT absorption band from 361 to 482 nm in CH2Cl2 and 487 nm in toluene, respectively. Thermal decomposition of the cationic complex [Cp2TiMe]+B(C6F5)4 - leads to less activity. The systems are good catalysts for ethylene polymerization as well, but are less active when using propylene. A conventional Ziegler-Natta coordination polymerization mechanism accounts for ethylene and propylene polymerization while a carbocationic polymerization mechanism is proposed for styrene.

Exchange chemistry of tBu3P(CO2)B(C6F 5)2Cl

Halide exchange from the species tBu3P(CO2)B(C 6F5)2Cl 1 with Me3SiOSO 2CF3 gave tBu3P(CO2)B(C 6F5)2(OSO2/

Synthesis and properties of [Cp2Ti(Me)(H2O)][B(C 6F5)4]

Treatment of water-stable Cp2TiMe2 with [Ph 3C][B(C6F5)4] in CD 2Cl2 gives the solvent-separated ion pair [Cp 2Ti(Me)(CD2Cl2)][B(C6F 5)4], which reacts rapidly with water at 205 K to give the corresponding aqua complex [Cp2Ti(Me)(H2O)][B(C 6F5)4]. The latter has been characterized by 1H and 13C NMR spectroscopy at 205 K and is a rare, possibly unique, example of a complex containing aqua and methyl ligands within the coordination sphere of a titanium(IV) complex.

Experimental and DFT Studies of cationic imido titanium alkyls: Agostic interactions and C-H bond and solvent activation reactions of isoiobal analogues of group 4 metallocenium cations

Synthesis, reactions, and DFT studies of macrocycle-supported imido titanium alkyl cations derived from Ti(NtBu)(Me3[9] aneN3)R2 (R = Me (1) or CH2SiMe3 (2)) are described (Me3[9]aneN3 = 1,4,7- trimethyltriazacyclononane). Reaction of 1 with 1 equiv of [Ph 3C][BAr4F] or BAr3F (ArF = C6F5) in C6D5Br afforded the methyl cation [Ti(NtBu)(Me3[9]aneN 3)Me]+ (6+), whereas with half an equivalent of [Ph3C][BAr4F] the fluxional methyl-bridged homo-binuclear cation [Ti2(NtBu)2(Me 3[9]aneN3)2Me2(μ-Me)] + (10+) was formed. Reaction of 1 with [Ph 3C][BAr4F] in CD2C12 formed the monochloride cation [Ti(NtBu)(Me3[9]aneN 3)Cl]+ (8+), which was also prepared from Ti(NtBu)(Me3[9]aneN3)Cl(Me) and [Ph 3C][BAr4F]. Cation 8+ reacted with pyridine to give the adduct [Ti(NtBu)(Me3[9]aneN 3)Cl(py)]+ (9+) and with Ti(N tBu)(Me3[9]aneN3)Me2 to form the chloride-bridged cation [Ti2(NtBu)2(Me 3[9]aneN3)2- Me2(μ-Cl)] + (11+). Reaction of 2 with [Ph3C][BAr 4F] gave [Ti(NtBu)(Me3[9]aneN 3)(CH2SiMe3)]+ (7+), which is stabilized by a β-Si-C agostic interaction characterized by a high-field-shifted 29Si NMR resonance. Attempts to generate 7 + by reaction of 2 with [PhNMe2H][BAr4 F] in CH2C12 led to Ti(NtBu)(Me 3[9]aneN3)Cl2 and [PhNMe2(CH 2Cl)][BAr2F] (12-BAr4F) via a series of solvent activation reactions, the details of which have been elucidated. Reaction of 6+ or 7+ with Ph3PO afforded the adducts [Ti(NtBu)(Me3[9]aneN 3)R(Ph3PO)]+, whereas with pyridine a C-H bond activation reaction occurred to give Ti(NtBu)(Me3[9] aneN3(NC5H4)]+ (17+) and the corresponding alkane RH. Density functional theory calculations of the isolobal d0 fragments [Ti(NR)(R′3[9]aneN 3)]2+ and [Cp2Ti]2+ found that their frontier orbitals, although broadly similar, featured important differences in their shapes and energies. These account for the absence of any α-C-H agostic interaction in 6+, whereas [Cp2TiMe]+ is stabilized by a weak interaction of this type as judged by DFT-computed geometries. The experimentally observed increase in Ti-Me group average 1JCH on forming either 6+ from 1 or [Cp 2TiMe]+ from Cp2TiMe2 is reproduced by DFT and attributed to intrinsic global changes in carbon 2s orbital contribution to the Ti-C and C-H bonds upon cation formation. These changes were shown to mask the otherwise expected decrease in average 1J CH for the α-agostic methyl in [Cp2TiMe] +. The difference between the Ti-Me 1JCH values in 1 (111 Hz) and isolobal Cp2TiMe2 (124 Hz) was also attributed to differences in Ti center electrophilicity. The experimental high-field-shifted 29Si NMR resonance in 7+ was well reproduced in the DFT-computed β-Si-C agostic structure, and upper and lower limits for the strength of the agostic interaction were estimated. An NBO analysis of the Ti-CH2SiMe3 bonding found several different contributions, including negative hyperconjugation (population of σ*(Siβ-Cγ)) and formal C α-Siβ→Ti and Siβ-C γ→Ti bond pair donation.