Rhodium‐Catalyzed C−H Activation Enabled by an Indium Metalloligand

Abstract

Rhodium complexes with an indium metalloligand were successfully synthesized by utilizing a pyridine‐tethered cyclopentadienyl ligand as a support for an In−Rh bond. The indium metalloligand dramatically changes the electronic and redox properties of the rhodium metal, thereby enabling catalysis of sp2C−H bond activation.

Catalysis using transition metal complexes featuring main group metal and metalloid compounds as supporting ligands

“…A Cp–rhodium complex 61 having a cationic InCl 2 + metalloligand was synthesized through the reaction of 2 equivalents of InCl 3 and a Rh I complex 60 , which was prepared from a pyridine-tethered Cp derivative 59 ( Scheme 26 ). 63 This method enables post-introduction of a group 13 metalloligand to a Cp–metal complex to form an M–E bond, which is distinct from the pre-introduction approaches described before. Therefore, screening of metalloligands becomes possible for the development of catalytic reactions.…”

Alternative Conceptual Approach to the Design of Bifunctional Catalysts: An Osmium Germylene System for the Dehydrogenation of Formic Acid

“… 7 Unfortunately, the number of Z-type ligands is notably limited 8 and as a consequence the reactions employing catalysts of this class are still very scarce. Metal Lewis bases mainly involve 3d metals, with iron, 9 cobalt, 10 and nickel 11 in prominent positions, in addition to rhodium, 12 palladium, 13 platinum, 14 and gold. 15 The Lewis acid site of the ligands is boron 9 , 10a − 10c , 11b − 11d , 13a , 15b , 15d in the great majority of the cases and to a much lesser extent aluminum, 11a 15a gallium, 11e 11f indium, 12 silicon, 13b and antimony.…”

Rational design of the nickel‐borane complex for efficient hydrogenation of styrene

“…In the past two decades, a series of M‐LA complexes with various metals (Pt, Pd, Rh, Au, Ir, Ru, Ni, Fe, Co, etc. ) 4–12 and LA atoms (B, Al, 4a,13 Ga, 14 In, 6a,14 etc.) have been reported (see Scheme 1), however, only several catalytic reactions mediated by M‐LA catalysts were reported in the literatures, such as hydrogenation, hydroamination, and hydrosilylation reactions.…”

“…have been reported (see Scheme 1), however, only several catalytic reactions mediated by M‐LA catalysts were reported in the literatures, such as hydrogenation, hydroamination, and hydrosilylation reactions. 2a,g,4–14 …”