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
1Department of Chemistry,
Moscow State University, Leninskie Gory, Moscow, 119899, Russia; 2N.
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.
* Lecture presented at the XIXth International Conference
on Organometallic Chemistry (XIX ICOMC) , Shanghai, China, 23-28 July
2000. Other presentations are published in this issue, pp. 205-376.
** Corresponding author
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