An emerging area of homogeneous catalysis is the use of catalysts featuring two closely
associated metal sites. This approach complements the traditional focus on single‐site
catalysts and makes available new parameters with which to optimize catalytic behavior.
Single‐site catalysts are optimized through changing 1) the identity of the metal, and 2) the
steric and electronic properties of the ligands. Bimetallic catalysts introduce new
optimization parameters such as 3) catalyst nuclearity (mononuclear vs. binuclear), and 4) …

Abstract Design of new bimetallic catalysts requires an understanding of how cooperative
effects of the metal sites influences reactivity. Here we show how switching one or both of
the silver atoms in binuclear silver hydride cations,[dppmAg2 (H)]+(dppm= 1, 1‐Bis
(diphenylphosphino)‐methane), with all combinations of copper and/or gold maintains
selective dehydrogenation of formic acid, enhancing reactivity by up to 2 orders of
magnitude. This is a key step in the selective, catalyzed extrusion of carbon dioxide from …