Twenty-five years of dimethylsulfoxonium ethylide (corey's reagent)
1987; Elsevier BV; Volume: 43; Issue: 12 Linguagem: Inglês
10.1016/s0040-4020(01)86869-1
ISSN1464-5416
AutoresYU. G. GOLOLOBOV, A. N. Nesmeyanov, V. Lysenko, I. E. Boldeskul,
Tópico(s)Organometallic Complex Synthesis and Catalysis
ResumoThe insoluble, yellow dimeric palladium compound [PdI{κ2C-(CH2)2SO(Me)}]2 reacts with ammonia solutions to form the colourless ammine complex cis-[Pd(NH3)I{κ2C-(CH2)2SO(Me)}]. Although this material readily reconverts to the parent dimer, crystals for a structure determination could be obtained. The ammonia ligand in this compound can be displaced by Ph3P or it can function as a "built-in" base to deprotonate species with acidic protons. The latter reactivity has been observed with acylchalcogenoureas. Imidazolium salts however did not react with the ammine complex directly. They were accessible from the reaction of the parent dimer with the azolium salts in the presence of base. X-rax structures of several examples are reported and DFT calculations were used to elucidate the electronic structure of the ylide ligand and the bonding interactions with the palladium atom.
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