E–H Bond Activations and Hydrosilylation Catalysis with Iron and Cobalt Metalloboranes

An exciting challenge in transition metal catalyst design is to explore whether earth-abundant base metals such as Fe, Co, and Ni can mediate two-electron reductive transformations that their precious metal counterparts (e.g., Ru, Rh, Ir, and Pd) are better known to catalyze. Organometallic metalloboranes are an interesting design concept in this regard because they can serve as organometallic frustrated Lewis pairs. To build on prior studies with nickel metalloboranes featuring the DPB and ^PhDPB^Mes ligands in the context of H₂ and silane activation and catalysis (DPB = bis­(<i>o</i>-diisopropylphosphinophenyl)­phenylborane, ^PhDPB^Mes = bis­(<i>o</i>-diphenylphosphinophenyl)­mesitylborane), we now explore the reactivity of iron, [(DPB)­Fe]₂(N₂), <b>1</b>, and cobalt, (DPB)­Co­(N₂), <b>2</b>, metalloboranes toward a series of substrates with E–H bonds (E = O, S, C, N) including phenol, thiophenol, benzo­[<i>h</i>]­quinoline, and 8-aminoquinoline. In addition to displaying high stoichiometric E–H bond activation reactivity, complexes <b>1</b> and <b>2</b> prove to be more active catalysts for the hydrosilylation of ketones and aldehydes with diphenylsilane relative to (^PhDPB^Mes)­Ni. Indeed, <b>2</b> appears to be the most active homogeneous cobalt catalyst reported to date for the hydrosilylation of acetophenone under the conditions studied