New metallocenes of early transition metals with functional groups in organic ligands. Red-ox transformations

Krut'ko, Dmitrii P.; Borzov, Maxim V.; Veksler, Edward N.; Kirsanov, Roman S.; Churakov, Andrej V.; Lemenovskii, Dmitri A.

doi:10.1351/pac200173020367

Pure Appl. Chem., 2001, Vol. 73, No. 2, pp. 367-371

http://dx.doi.org/10.1351/pac200173020367

New metallocenes of early transition metals with functional groups in organic ligands. Red-ox transformations

Dmitrii P. Krut'ko¹, Maxim V. Borzov¹, Edward N. Veksler¹, Roman S. Kirsanov¹, Andrej V. Churakov²* and Dmitri A. Lemenovskii¹

¹ Department of Chemistry, Moscow State University, Leninskie Gory, Moscow, 119899, Russia
² N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Science, Leninskii prospect 31, Moscow, 117907, Russia

Abstract: The reduction behavior of the novel zirconocene dichlorides, (h5-C₅Me₅) (h⁵-C₅Me₄CH₂CH₂ER₂) ZrCl₂ (ER₂ = NMe₂, PMe₂, PPh₂) , (h⁵-C₅Me₄CH₂ CH₂PMe₂) ₂ZrCl₂, and (h⁵-C₅Me₄CH₂ CH₂PPh₂) (h⁵-C₅Me₄CH₂CH₂PMe₂) ZrCl₂, together with the new types of intramolecular activation of inert C-H and C-heteroatom bonds are presented and discussed. A remarkably thermally stable zirconocene alkylhydryde type framework complex (h⁵-C₅Me₅) [h⁵ ,s-C₅Me₄CH₂CH₂N (Me) CH₂-]ZrH, zirconocene arylhydryde complex (h⁵-C₅Me₅) [h⁵ ,s-C₅Me₄CH₂CH₂P (Ph) -o-C₆H₄-]ZrH, tetramethylfulvene hydride-type complexes (h⁵-C₅Me₅) [h⁶ :h¹- (CH₂C₅Me₃ ) CH₂CH₂PR₂]ZrH (R = Me, Ph) and (h⁵-C₅Me₄CH₂ CH₂PPh₂) [h⁶:h¹- (CH₂C₅Me₃) CH₂CH₂PMe₂]ZrH are reported. The first unusually thermally stable zirconocene (h⁵,h¹-C₅Me₄ CH₂CH₂PMe₂) ₂ Zr with the Zr (II) center stabilized by intramolecular coordination of two Me₂P-groups is described.