NDLI: Reduction of bis[(2-phosphinoethyl)tetramethyl-cyclopentadienyl]zirconium dichlorides: intramolecular C-H activation vs. stabilization of the low-valence metal center

Content Provider	SpringerLink
Author	Krut’ko, D. P. Borzov, M. V. Veksler, E. N. Kirsav, R. S.
Copyright Year	2008
Abstract	Reduction of the R$_{2}$P-functionalized zirconocene dichlorides [C$_{5}$Me$_{4}$(CH$_{2}$)$_{2}$PR$_{2}$] (C$_{5}$Me$_{5}$)ZrCl$_{2}$ (R = Me (1) and Ph (2)) and [C$_{5}$Me$_{4}$(CH$_{2}$)$_{2}$PMe$_{2}$][C$_{5}$Me$_{4}$(CH$_{2}$)$_{2}$PR$_{2}$]ZrCl$_{2}$ (R = Me (3) and Ph (4)) with amalgamated magnesium was studied. In the reduction of compounds 1 and 2, intramolecular C-H activation highly selectively afforded the fulvene hydride complexes Zr(H)(η$^{5}$−C$_{5}$Me$_{5}$)[η$^{5}$:η$^{2}$(C,P)−(CH$_{2}$)C$_{5}$Me$_{3}$CH$_{2}$CH$_{2}$PR$_{2}$] (R = Me (7), Ph (8)); in the case of compound 2, the aryl hydride Zr(H)(η$_{5}$:C$_{5}$Me$_{5}$)[η$^{5}$:η$^{1}$(C)−C$_{5}$Me$_{4}$CH$_{2}$CH$_{2}$PPh(o−C$_{6}$H$_{4}$)] (9) was also formed. The reduction of complexes 3 and 4 gave the Zr$^{II}$ derivatives Zr[η$^{5}$:η$^{1}$(P)− C$_{5}$Me$_{4}$CH$_{2}$CH$_{2}$PMe$_{2}$]$_{2}$ (12) and Zr[η$^{5}$:η$_{1}$(P)−C$_{5}$Me$_{4}$CH$_{2}$CH$_{2}$PMe$_{2}$][η$^{5}$:η$^{1}$(P)−C$_{5}$Me$_{4}$CH$_{2}$ CH$_{2}$PPh$_{2}$] (14) stabilized by two phosphine groups. The second product in the reduction of compound 4 was the fulvene hydride complex Zr(H)(η$^{5}$−C$_{5}$Me$_{4}$CH$_{2}$CH$_{2}$PPh$_{2}$)[η$^{5}$:η$^{2}$(C,P)−(CH$_{2}$)C$_{5}$Me$_{3}$CH$_{2}$CH$_{2}$PMe$_{2}$] (15). The reaction of compound 7 with an excess of MeI resulted selectively in replacement of the hydride ligand by iodide to give the complex ZrI(η$^{5}$−C$_{5}$Me$_{5}$)[η$^{5}$:η$^{2}$(C,P)−(CH$_{2}$)C$_{5}$Me$_{3}$CH$_{2}$CH$_{2}$PMe$_{2}$] (10). In contrast, in the reaction of compound 7 with Me$_{2}$Si(H)Cl, the Zr-CH$_{2}$ bond underwent cleavage to give the chloride hydride complex Zr(H)Cl(η$_{5}$−C$_{5}$Me$_{5}$)[η$^{5}$:η$^{1}$(P)−C$_{5}$Me$_{3}$(CH$_{2}$SiMe$_{2}$H)CH$_{2}$CH$_{2}$PMe$_{2}$] (11). In the reaction of complex 12 with CO, a phosphine group was replaced by CO to form the complex Zr(CO)(η5−C$_{5}$Me$_{4}$CH$_{2}$CH$_{2}$PMe$_{2}$)[η$^{5}$:η$^{1}$(P)−C$_{5}$Me$_{4}$CH$_{2}$CH$_{2}$PMe$_{2}$] (13). The results obtained were compared with analogous reduction reactions of MeO-, MeS-, and Me$_{2}$N-functionalized zirconocene dichlorides.
Starting Page	68
Ending Page	77
Page Count	10
File Format	PDF
ISSN	10665285
Journal	Russian Chemical Bulletin
Volume Number	57
Issue Number	1
e-ISSN	15739171
Language	English
Publisher	Springer US
Publisher Date	2009-01-10
Publisher Place	Boston
Access Restriction	Subscribed
Subject Keyword	zirconium cyclopentadienyl ligands phosphine ligands reduction intramolecular C-H activation intramolecular coordination fulvene hydride complexes NMR spectroscopy Inorganic Chemistry Organic Chemistry Chemistry/Food Science
Content Type	Text
Resource Type	Article
Subject	Chemistry

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