Tetracarbonylcyclopentadienyl Compounds of the Group V Transition Metals

An investigation of the reaction of bis(cyclopentadienyl)titanium dichlorides with trimethylaluminum. Mechanism of an .alpha.-hydrogen abstraction reaction

“…The solids were washed several times with cold ether and dried to yield 2.1-2.4 g (80-90%) of a mixture of Cp'CpTiCl2 which typically contained 10-20% of both Cp2TiCl2 and Cp'2TiCl2. Fractional crystallization of this mixture from hot toluene yielded 60-70% Cp'CpTiCl2 as red needles which contained approximately [5][6][7][8][9][10] Performing the reaction at room temperature or with a 50% excess of Cp'Li results in near statistical mixtures of Cp2TiCl2, Cp'CpTiCl2, and Cp'2TiCl2. NMR (CDC13) 6.54 (s, Cp), 6.73 (m, C-AMe), 2.33 (s,C6H4Me).…”

“…Preparation of [CB(CH3)5]CpTiCl2 (6). A suspension of CpLi (0.72 g, 10 mmol) in 10 mL of THE was added slowly via cannula to a stirred solution of Cp*TiCl3 (2.9 g, 10 mmol) in 10 mL of THE under an Ar atmosphere at ambient temperature.…”

“…That the aluminum halide bond polarization in these reactions is important is indicated by the very rapid formation of Cp2TiMe2 and AlMe2F from the reaction of Cp2TiF2 with 4 equiv of AlMe3. Apparently, the position of equilibrium of eq 6 lies in the center for X = Cp2TiX2 + 2AlMe3 ^Cp2TiMeX-Al Ĉp2TiMe2 + 2AlMe2X (6) titanium methylehe formation reation, the mixed-ring compounds were synthesized and the kinetics of their reaction with AlMe3 measured. These data are tabulated in Table V and appear in order of increasing size of the substituted cyclopentadienyl ligand.…”

“…In the mid-1960's several groups studied the reaction of Cp2TiCl2 with AlMe3 and noticed that methane was evolved and that the organometallic product contained Ti-CH2-Al units. 6 Tebbe and Parshall6 reinvestigated this system and purified the titanium methylene complex Cp2Ti-CH2AlMe2Cl (1) and other derivatives.…”

Cyclomer complexes. Crystal structure of a 2:1 pentahydrate complex of 1,4,7,10-tetraoxacyclododecane with sodium chloride [Na+(C8H16O4)2][Cl-.5H2O]

“…9.9 (1.5) H(122) 0.164 (2) 0.352 (4) 0.214 (3) 4.4 (0.9) °Standard errors are given in parentheses. 6 The anisotropic temperature factors are given by the expression exp[-(0n/i2 + 022k2 + 03312 4• 2012/ik + 2013/zZ + 2023kZ)j.…”