Abstract

Highly regio- and stereoselective dimerization of terminal acetylenes occurs in the presence of [PdCl2(IPr)(3-chloropyridine)], other members of the family of PEPPSI precatalysts and the structurally related N-heterocyclic carbene palladium dimers, i.e. [{Pd(μ–Cl)Cl(IPr)}2] and [{Pd(μ–OH)Cl(IPr)}2] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene). The reaction leads to exclusive formation of E-isomer of head to head dimerization product. [{Pd(μ–OH)Cl(IPr)}2] catalyzes dimerization of a broad spectrum of aryl- and silylacetylenes at room temperature and is able to act in base-free conditions.

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