The reaction of (η5-C5H4SiMe3)2TiCl2 (1) with HO(CH2)nC ≡ CR (2a: n = 1, R = H; 2b: n = 1, R = CH3; 2c: n = 1, R = CH2OH ; 3: n = 2, R = H; 4: n = 4, R = H) affords in toluene at 25 °C in the presence of NEt3 the monoalkyne-ol substituted titanocenes (η5-C5H4SiMe3)2Ti(Cl)[O(CH2)nC ≡ CR] (5a: n = 1. R = H; 5b: n = 1, R = CH3; 5c: n = 1, R = C H2OH; 6: n = 2, R = H; 7: n = 4. R = H ). Compound 5c reacts with one equivalent of 1 in the presence of NEt3 to yield (η5-C5H4SiMe3)2(Cl)Ti-OCH2C ≡ CCH2O -Ti(Cl)(η5-C5H4SiMe3)2 (8). In addition, compound 8 can be synthesized directly by treatment of (η5- C5H4SiMe3)2TiCl2 (1) with 0.5 equivalents of HOCH9C≡CCH2OH (2c) in the presence of NEt3. The reaction of (η5-C5H4SiMe3)2Ti(Cl)(OCH2C ≡ CCH3) (5b) with Co2(CO)8 (9) yields (η5-C5H4SiMe3)2Ti(Cl)[(η2-OCH2C ≡ CCH3)Co2(CO)6] (10). Treatment of 5b or 10 with HCl(aq) (11) leads to the formation of (η5-C5H4SiMe3)2TiCl2 (1) and HOCH2C ≡ CCH3 (2b) (reaction of 5b with 11) or (η5-C5H4SiMe3)2TiCl2 (1) and [(η2-HOCH2C ≡ CCH3)Co2(CO)6] (12) (reaction of 10 with 11). All compounds have been characterized by analytical and spectroscopic data (IR , 1H, 13C NMR, MS) and (η5-C5H4SiMe3)2Ti(Cl)(OCH2C ≡ CCH3) (5b) by X -ray analysis.
An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. III. The Profile of SKβ Band in Sulfur Compounds