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

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-C 5Me4CH2CH2ER 2) ZrCl2 (ER2 = NMe2, PMe2, PPh2) , (h5-C5Me4CH2 CH2PMe2) 2ZrCl 2, and (h5-C5Me4CH2 CH2PPh2) (h5-C 5Me4CH2CH2PMe 2) 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-C5Me4CH2CH 2N (Me) CH2-]ZrH, zirconocene arylhydryde complex (h5-C5Me5) [h5 ,s-C5Me4CH2CH 2P (Ph) -o-C6H4-]ZrH, tetramethylfulvene hydride-type complexes (h5-C5Me5) [h6 :h1- (CH2C5Me3 ) CH2CH2PR2]ZrH (R = Me, Ph) and (h5-C5Me4CH2 CH2PPh2) [h6:h 1- (CH2C5Me3) CH 2CH2PMe2]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.