Organometallics 1994,13, 4751-4764
4751
Carbon-Carbon Coupling Reactions between Metallacarbynes Cp(CO)m=CR and Cyclopalladated Ligands: Synthesis of a Novel Class of Palladium p-Alkylidene Complexes Philippus F. Engel and Michel Pfeffer* Laboratoire de Synthbes Mitallo-induites (URA41 6 d u CNRS), Universiti Louis Pasteur, 4, rue Blaise Pascal, F-67070 Strasbourg Cedex, France
J. Fischert Laboratoire de Cristallochimie (URA424 d u CNRS), Universiti Louis Pasteur, 4, rue Blaise Pascal, F-67070 Strasbourg Cedex, France Received June 17, 1994@
The carbyne carbon atom of metallacarbynes such a s (q5-C5H5)(CO)2M=CR (where M = Mo, W and R = p-tolyl, 4-tert-butylphenyl, 2,6-dimethylphenyl, 1-cyclopentenyl) is readily coupled with the palladated carbon atom of various cyclopalladated compounds. This reaction affords good to excellent yields of novel p-alkylidene complexes whose structure is maintained irrespective of the palladated ligand employed. For example, the reaction of (v5-C5H5)(C0)2Mo=C-p-Tol with [2-MezNCH~C6WdCl12 affords [2-Me2NCH2C6H4(q3-@-C@-Tol)Mo+-CO)}C5H5(CO)PdCl].
Introduction Carbon-carbon coupling reactions of metallacarbynes (of the type L~MECR,M = d5 metal) are well-known, although the most general reactions occur mainly in the presence of three types of reagents: tertiary phosphines, protic acids, and a1kynes.l Tertiary phosphines induce coupling between the carbyne ligand C(R) and a carbonyl ligand, resulting in ketenyl complexes. Protonation leads to the coupling of two carbyne ligands to form bimetallic complexes with bridging alkyne ligands. Alkynes react in the presence of protons to form a series of naphthol ligands, which can be easily separated from the metal. C-C coupling reactions between these metallacarbynes and organometallic substrates are much less common, and no truly general reaction has yet been reported. The known examples include the phenyl and alkyl complexes Cr(Ph)s(thf)a and ZnR2 (R = Ph, Pr, C H ~ - ~ - Tand O ~the ) ~bimetallic Tebbe reagent. This last compound transfers its bridging methylene group onto the carbyne carbon, which corresponds to the formal insertion of the carbon atom of the triple bond into the titanium-carbon bond (eq l).3a
,CH2
+ CpzTi
Cp(CO),W=C-To1
‘AIMe,
C ‘’l
;.
