Additive‐Free Formic Acid Dehydrogenation Using a Pincer‐Supported Iron Catalyst

Abstract

The iron complex (iPrPNMeP)Fe(H)2(CO) (iPrPNMeP=CH3N(CH2CH2PiPr2)2), which features a pincer ligand with a tertiary amine, can give up to 100,000 turnovers for additive‐free formic acid dehydrogenation (FADH). This is two orders of magnitude higher than any previously reported base metal system. Mechanistic studies reveal the catalytic reaction pathway and provide guidance for the development of improved catalytic systems for additive‐free FADH.

Strong Metal–Support Interaction for 2D Materials: Application in Noble Metal/TiB2 Heterointerfaces and their Enhanced Catalytic Performance for Formic Acid Dehydrogenation

“…In aqueous phase, HCOOH dehydrogenation requires both catalysts and additives (e.g., ligands, additional bases, or Lewis acids) at elevated temperatures (>50 °C). [ 25 ] Here, we show that the TiB 2 ‐based catalysts can efficiently catalyze HCOOH dehydrogenation at room temperatures, without any additive.…”

HCOOH disproportionation to MeOH promoted by molybdenum PNP complexes

“…Additionally, we considered whether the ability to promote HCOOH disproportionation beside dehydrogenation is characteristic for molybdenum or might be instead achieved with other metals supported by the aliphatic PNP ligand ( Scheme 3 ). Thus, pincer complexes of Ru, 10 , 30 Ir, 11 , 31 Mn, 12 32 as well as Fe, 13 33a,b and 14 , 33 were selected which would require no additive to generate an active catalytic species ( Scheme 3 ). However, under the applied reaction conditions, only the ruthenium catalyst 10 promoted HCOOH dehydrogenation ( Table 2 , entry 8, total evolved gas volume 347 mL) but in no case methanol or methyl formate were detected.…”

Additive-Free Formic Acid Dehydrogenation Catalyzed by a Cobalt Complex

“…21 Beller et al pioneered the use of iron complexes in 2010, and a number of PNP pincer ligands chelated to an iron centre have been reported since. [22][23][24][25][26][27][28][29][30][31] Manganese complexes have also been reported to be active in this reaction, as reported by Boncella, Tondreau, et al and Beller et al. [32][33][34] The activity of other 3d metals was assessed over the past few years, using nickel (Junge, Enthaler et al and Parkin et al), 35,36 copper (Correa et al), 37 and cobalt (Beller et al and Onishi et al).…”