title: Novel Z-selective head-to-head dimerization of terminal alkynes catalyzed by lanthanide half-metallocene complexes.
abstract: Various terminal alkynes have been cleanly dimerized into the corresponding head-to-head (Z)-enynes by use of the half-metallocene lutetium alkyl complexes Me2Si(C5Me4)(NAr)Lu(CH2SiMe3)(THF) (Ar = Ph, C6H3Me2-2,6, C6H2Me3-2,4,6) as catalysts. Aromatic C-Cl, C-Br, and C-I bonds, which are known to be extremely susceptible to reductive cleavage by transition metals, survived in the present reactions. The corresponding dimeric alkynide species [Me2Si(C5Me4)(NAr)Lu(mu-CCR)]2 are thought to be the true catalysts, some of which have been isolated and structurally characterized. These alkynide species were thermally stable and soluble at the reaction temperatures (80-110 degrees C), but they precipitated upon cooling to room temperature after completion of the reaction. Therefore, this catalyst system works homogeneously but can be separated and reused, thus constituting the first example of a recyclable catalyst system for the dimerization of terminal alkynes and also the first example of (Z)-selective head-to-head dimerization of aromatic terminal alkynes.
authors.affiliation: Organometallic Chemistry Laboratory, RIKEN (The Institute of Physical and Chemical Research), Hirosawa 2-1, Wako, Saitama 351-0198, Japan.
authors.forename: Masayoshi
authors.initials: M
authors.lastname: Nishiura
authors.forename: Zhaomin
authors.initials: Z
authors.lastname: Hou
authors.forename: Yasuo
authors.initials: Y
authors.lastname: Wakatsuki
authors.forename: Taeko
authors.initials: T
authors.lastname: Yamaki
authors.forename: Takeshi
authors.initials: T
authors.lastname: Miyamoto