138901-63-0Relevant academic research and scientific papers
Synthesis and Reactivity of ((η5-C5H4SiMe3)2Ti(CCPh)2)Ni(CO)
Lang, Heinrich,Imhof, Wolfgang
, p. 1307 - 1312 (2007/10/02)
The synthesis and reactivity of ((η5-C5H4SiMe3)2Ti(CCPh)2)Ni(CO) (6) is described. (η5-C5H4SiMe3)2Ti(CCPh)2 (1a) reacts with equimolar amounts of Ni(CO)4 (5) to afford dinuclear complex ((η5-C5H4SiMe3)2Ti(CCPh)2)Ni(CO) (6) in 95percent yield.In 6 both phenylethynyl units are η2-side-on-coordinated to the Ni(CO) moiety.When 6 is reacted with HX or X2 (X = Cl, Br) the Ti-C(alkynyl) ? bond is cleaved, and the corresponding titanocene dihalides (η5-C5H4SiMe3)2TiX2 (7) are formed.With PRR'2 (8a: R = R' = OMe; 8b: R = CCPh, r' = Ph; 8c: R = Ph, R' = CCPh) 6 reacts by substitution of the nickel-bonded carbonyl ligand to form ((η5-C5H4SiMe3)2Ti(CCPh)2)Ni(PRR'2) (9).The reactivity of 9b, which contains a noncoordinated phenylethynyl unit, has been investigated by using Co2(CO)8 (10) and Fe2(CO)9 (13).With 10 the compounds ((η5-C5H4SiMe3)2Ti(CCPh)2)Ni(CO) (6), 2-Ph2PCCPh)>Co2(CO)6 (11) and (2-Ph2PCCPh)>Co2(CO)5)2 (12) can be obtained.Complex 11 yields upon heating by decarbonylation and dimerization the six-membered cyclic compounds 12.Whereas, the reaction of 9b with 13 affords ((η5-C5H4SiMe3)2Ti(μ-PPh2)1:η2-CCPh)> (14).Key Words: Titanocenes / Alkynyl ligands / Titanium complexes / Nickel complexes
