96454-41-0Relevant academic research and scientific papers
SYNTHESIS AND STRUCTURE OF ; INFLUENCE OF THE FUNCTIONAL GROUP ON THE NATURE AND STABILITY OF THEIR d1 REDUCTION PRODUCT
Bailey, Stuart I.,Colgan, Daryl,Engelhardt, Lutz M.,Leung, Wing-Por,Papasergio, Rocco I.,et al.
, p. 603 - 614 (2007/10/02)
Reaction of with organolithium reagents Li(tmen) (Rn) = a highly hindered alkyl, CHSiMe3C5H4N-2 (R1), CHSiMe3C6H4PPh2-o (R2), CHSiMe3(C14H9-9) (R3) (C14H9 = anthryl), or CHSiMe3(C6H4Me-p) (R4; tmen = Me2NCH2CH2NMe2> in tetrahydrofuran (thf) yields n)Cl(η-C5H5)2>, compounds (2), (4), (6), and (8), respectively.Electrochemical reduction of (6) is reversible (10 1/2 1 species, respectively 1)(η-C5H5)2>, with R1 chelating or η3-aza-allyl, and (31P coupling) either in thf (Na or toluene (Na/Hg).Reduced (2), (4), (6), and (8) react with PMe3 yielding d1 n)(PMe3)-(η-C5H5)2>.Variable-temperature 1H n.m.r. investigation of (2) in toluene shows an equilibrium between four and five-co-ordinate complexes; in the solid the latter prevails with a Zr-N distance of 2.341 Angstroem, and an exceptionally long Zr-Cl distance (2.563 Angstroem).In (4) the functional group is not bound to the metal centre and in (6) the potentially ambidentate alkyl R3 is bound through the benzylic carbon .
