- Cationic alkylbis(cyclopentadienyl)titanium complexes. Synthesis, reactions with CO and t-BuNC, and the structure of [Cp2Ti{η2-C(Me)N-t-Bu}(CN-t-Bu)]BPh 4·MeCN
-
Cationic methylbis(cyclopentadienyl)titanium complexes [Cp2TiMe(L)]BPh4 (L = MeCN, n-PrCN, t-BuCN, PhCN, PMe3, PMe2Ph, PMePh2, n-Bu3P, pyridine) have been synthesized in high yields by reaction of Cp2TiMeCl with L and sodium tetraphenylborate in polar solvents. A range of bis(indenyl)titanium complexes is similarly accessible. The complex [Cp2TiMe(NCMe)]BPh4 reacts with carbon monoxide to give [Cp2Ti(η2-COMe)(NCMe)]BPh4 in which the nitrile ligand is retained, while tert-butyl isocyanide displaces acetonitrile and inserts into the titanium-methyl bond to give [Cp2Ti{C(N-t-Bu)Me}(CN-t-Bu)]BPh4·MeCN (18) whose crystal structure was determined. The complex crystallizes in space group P21/c, a = 13.212 (10) A?, b = 9.354 (2) A?, c = 33.951 (4) A?, β = 91.87 (4)°, V = 4193.3 A?3, Z = 4, and Dcalcd = 1.14 g cm-3. The iminoacyl ligand in 18 is η2-coordinated, with Ti-C and Ti-N distances of 2.08 and 2.12 A? and a short C=N bond (1.24 A?).
- Bochmann, Manfred,Wilson, Ladislav M.,Hursthouse, Michael B.,Short, Richard L.
-
p. 2556 - 2563
(2008/10/08)
-
- Synthesis and Insertion Reactions of Cationic Alkylbis(cyclopentadienyl)titanium Complexes
-
The electrophilic 14-electron alkyltitanium cations (+) (cp = η5-cyclopentadienyl) and (+) (ind = η5-indenyl), accessible via several routes, form stable complexes (+) and (+), L = NH3, PMe
- Bochmann, Manfred,Wilson, Ladislav M.
-
p. 1610 - 1611
(2007/10/02)
-