Synthesis of MAuAg (M = Ni, Pd, or Pt) and NiAuCu Heterotrimetallic Complexes Ligated by a Tritopic Carbanionic -Heterocyclic Carbene.

Heterotrimetallic complexes (NiAuAg, PdAuAg, PtAuAg, and NiAuCu) containing a tritopic -heterocyclic carbene (NHC) have been synthesized for the first time through the deprotonation and metalation of heterodimetallic complexes and were structurally characterized by single-crystal X-ray diffraction. The carbene character of the donor groups in the tritopic NHC complexes was established on the basis of structural and NMR analyses.

Syntheses of tetrahydroquinoline-based chiral carbene precursors and the related chiral NHC-Au(i) complex.

Four tetrahydroquinoline-based chiral carbene precursors were synthesized using unsymmetrical ,'-diarylformamidines and chiral 2-allyloxiranes as starting materials. A representative NHC-gold complex has been prepared and fully characterized, the crystal structure of which reveals an intramolecular Au⋯H-C(sp) interaction between Au(i) and the hydrogen atom of the isopropyl moiety in the -aryl group.

Pd-Promoted cross coupling of iodobenzene with vinylgold via an unprecedented phenyl transmetalation from Pd to Au.

A novel Pd/Au vinylene complex synthesized through cyclization of σ,π-heterodinuclear (Pd/Au) acetylide reacted with iodobenzene to give a Pd vinyl species, where the presence of a strong metallophilic PdAu interaction was found to facilitate phenyl transmetalation from Pd to Au, followed by reductive elimination at Au.