Transition metal alkynyl complexes by transmetallation from Au(CCAr)(PPh₃) (Ar = C₆H₅or C₆H₄Me-4)

Abstract

Facile acetylide transfer reactions take place between gold(I) complexes Au(C[triple bond]CAr)(PPh3) (Ar = C6H5 or C6H4Me-4) and a variety of representative inorganic and organometallic complexes MXL, (M = metal, X = halide, L, = supporting ligands) featuring metals from groups 8-11, to afford the corresponding metal-alkynyl complexes M(C[triple bond]CR)Ln in modest to good yield. Reaction products have been characterised by spectroscopic methods, and molecular structure determinations are reported for Fe(C[triple bond]CC6H4Me-4)(dppe)Cp, Ru(C[triple bond]CC6H4Me-4)(dppe)Cp*, Ru(C=CCsF,)(l2-O2)(PPh3)Cp*, Ir(C-CC6H4Me-4)(eta2-O2)(CO)(PPh3), Ni(C[triple bond]CC6H4Me-4)(PPh3)Cp and trans-Pt(C[triple bond]CAr)2L2 (Ar = C6H5, L = PPh3; Ar = C6H4Me-4, L = PPh3, PMe3).

New rhodium(I) supramolecular structures containing pyridyl and bipyridyl ligands

“…Similar processes involving alkynyl ligands and gold(I) metal atoms are known but still scarce [42][43][44][45]. In particular, the transmetallation reaction where an ethynylpyridine group is transferred from a gold(I) metal centre to a rhenium (I) complex, has been previously reported by us and being favoured by the formation of the same [Au(C"CC 5 H 4 N)] n polymer [45].…”

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

“…[76][77][78] In this case, the gold serves as a transmetallation agent, and the use of a pre-formed Au I complex permits the transfer of the alkynyl or diynediyl species to Pd II under mild conditions. [79] In this manner, differentially substituted 1,3-diynes can be prepared by the sequential cross-coupling of each Au-alkynyl moiety in Ph 3 PAuCϵCCϵCAuPPh 3 (Scheme 4); similar Au-mediated transmetallation chemistry has been used in conjunction with Pd/Cu cycles in the synthesis of metal complexes featuring polyyn(di)yl ligands of considerable length.…”

Bimetallic Catalysis using Transition and Group 11 Metals: An Emerging Tool for CC Coupling and Other Reactions

“…In fact, many examples have been reported of transmetalation of ethynyl groups from gold complexes to other metals, such as Hg and Pt, [14] Ni, [15] Re, [16] U, [17] Fe, Ru, and Ir, [18] or Pd [19] (Scheme 5). Less frequently, silver complexes have also been used as ethynylating agents towards Pt and Pd complexes.…”