title: Reactions of group 4 metallocene alkyne complexes with carbodiimides: experimental and theoretical studies of the structure and bonding of five-membered hetero-metallacycloallenes.
abstract: The reaction of the low-valent metallocene(II) sources Cp(2)Ti(η(2)-Me(3)SiC(2)SiMe(3)) (7) and Cp(2)Zr(py)(η(2)-Me(3)SiC(2)SiMe(3)) (11, Cp = η(5)-cyclopentadienyl, py = pyridine) with carbodiimides RN═C═NR (R = Cy, i-Pr, p-Tol) leads to the formation of five membered hetero-metallacycloallenes Cp(2)M{Me(3)SiC═C═C[N(SiMe(3))(R)]-N(R)} (9M-R) (M = Ti, R = i-Pr; M = Zr, R = Cy, i-Pr, p-Tol). Elimination of the alkyne (as the hitherto known reactivity of titanocene and zirconocene alkyne complexes would suggest) was not observed. The molecular structures of the obtained complexes were confirmed by X-ray studies. Moreover, the structure and bonding of the complexes 9Zr-Cy and 9Zr-p-Tol was investigated by DFT calculations.
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, D-18059 Rostock, Germany.
authors.forename: Katharina
authors.initials: K
authors.lastname: Kaleta
authors.forename: Martin
authors.initials: M
authors.lastname: Ruhmann
authors.forename: Oliver
authors.initials: O
authors.lastname: Theilmann
authors.forename: Torsten
authors.initials: T
authors.lastname: Beweries
authors.forename: Subhendu
authors.initials: S
authors.lastname: Roy
authors.forename: Perdita
authors.initials: P
authors.lastname: Arndt
authors.forename: Alexander
authors.initials: A
authors.lastname: Villinger
authors.forename: Eluvathingal D
authors.initials: ED
authors.lastname: Jemmis
authors.forename: Axel
authors.initials: A
authors.lastname: Schulz
authors.forename: Uwe
authors.initials: U
authors.lastname: Rosenthal