Ag(I)-Induced C-C Reductive Elimination from Pt(II): Role of Ag(I) and Counteranion
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Published on: July 12, 2016
Md Asmaul Hoque1, Zoë M Gehman1, Farzad Bastani2
1Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States.
Abstract:
Transition-metal-catalyzed C-C bond formation, including C-H functionalization reactions, often benefits from Lewis acid additives, among which Ag-(I) salts are widely used in Pd-catalyzed transformations. Despite this, direct experimental evidence defining the mechanistic role of Lewis acid additives remains limited. Herein, we investigate the role of Ag-(I) additives in C-C bond formation using (6-Fp)-PtPh2 (1) (6-Fp = 8,8'-(1,2-phenylene)-diquinoline) as the starting complex. The reaction of (6-Fp)-PtPh2 with different Ag-(I) compounds gives significantly different yields for the formation of biphenyl. Unexpectedly, our combined experimental, including 195Pt NMR spectroscopy and X-ray photoelectron spectroscopy, and computational studies reveal that Ag-(I) becomes incorporated into the Pt bonding framework to form multimetallic Pt/Ag intermediates that can promote reductive elimination. The Ag-(I) counteranion strongly influences the structure and reactivity of these intermediates, giving the rate trend AgTFA ≈ AgOTf > AgNO3 for the formation of biphenyl. These findings provide direct evidence for multimetallic cooperation involving Ag-(I) in C-C bond formation.
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