Double-insertion reaction of alkynes with [CP{sup {prime}}{sub 2}ZrMe]{sup +}: Formation of an unusual distorted {eta}{sup 5}-pentadienyl ligand

Journal Article · Wed Jan 01 04:00:00 EST 1992 · Organometallics

DOI:https://doi.org/10.1021/om00037a005· OSTI ID:263710

Horton, A D ^[1]; Orpen, A G ^[2]

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1. Koninklijke/Shell-Laboratorium, Amsterdam (Netherlands)
2. Univ. of Bristol (United Kingdom)

Reaction of [Cp{sup prime} {sub 2}ZrMe(NMe{sub 2}Ph)] [X] (1; Cp{sup prime} = C{sub 5}H{sub 5} (a), (Me{sub 3}Si)C{sub 5}H{sub 4}(b), (Me{sub 3}Si)C{sub 5}H{sub 4} (c), rac-C{sub 2}H{sub 4}(indenyl){sub 2} (d); [X]{sup {minus}} = [B(4-C{sub 6}H{sub 4}F{sub 4}]{sup {minus}}) with excess 2-butyne gives [Cp{sup prime} {sub 2}Zr({eta}{sup 5}-CH{sub 2}C(Me)=C(Me)C(Me)=CHMe)][X] (2a-d); an X-ray structure analysis of 2c shows that novel pentadienyl coordination occurs via a {sigma}-bond and two weak unconjugated {eta}{sup 2}-interactions with the double bonds. The reaction proceeds via observable, but unstable, alkenyl and 1,3-alkadienyl complexes, followed by a 1,5-hydrogen shift. Double alkyne insertion is unfavorable for crowded (C{sub 5}Me{sub 5}){sub 2}ZrMe(X), which instead gives [C{sub 5}Me{sub 5}){sub 2}Zr({eta}{sup 3}-CH{sub 2}C=CMe)][X] via a {sigma}-bond metathesis reaction. 25 refs., 1 fig.

• Sponsoring Organization: USDOE
• OSTI ID: 263710
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 1 Vol. 11; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ALKYNES
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
ORGANOMETALLIC COMPOUNDS
X-RAY DIFFRACTION
ZIRCONIUM COMPLEXES