title: Synthesis and reactions of a zirconium naphthalene complex bearing a tetraanionic C-capped triaryloxide ligand.
abstract: Treatment of [(O3C)Zr(thf)3] (1; [O3C]4-= [(3,5-tBu2-2-OC6H2)3C]4-) with 2 equiv. of potassium naphthalenide in DME produced [{K(dme)}2(O3C)Zr(C10H8)] (2), in which the [(O3C)Zr] fragment is η4-bound to one ring of the naphthalene ligand. Complex 2 underwent facile exchange with free naphthalene, and addition of anthracene into a solution of 2 resulted in clean formation of an anthracene complex [{K2(dme)3}(O3C)Zr(C14H10)] (3). The reaction of 2 with an excess of Me3SiN3involves generation of an imide intermediate via extrusion of N2and Si-N bond cleavage, and an amide complex [{K(thf)2}(O3C)Zr{N(SiMe3)2}(thf)] (4) was isolated. Analogously, treatment of 2 with mesityl azide (MesN3) followed by addition of Me3SiN3afforded [{K(thf)2}(O3C)Zr{N(Mes)(SiMe3)}(thf)] (5). Hydrogenation of 2 provided a hydride-bridged dizirconium complex [{K(thf)2}3{(O3C)Zr}2(μ-H)3] (6) along with tetralin. The solid-state structures of 2, 4, and 5 were established by single-crystal X-ray diffraction studies.
authors.affiliation: Department of Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8551, Japan. hkawa@chem.titech.ac.jp.
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Nakanishi
authors.affiliation: Department of Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8551, Japan. hkawa@chem.titech.ac.jp.
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Ishida
authors.affiliation: Department of Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8551, Japan. hkawa@chem.titech.ac.jp.
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Kawaguchi