Selective Catalytic Reduction of N₂ to N₂H₄ by a Simple Fe Complex

The catalytic fixation of N₂ by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for N₂H₄ production. Herein we report that the simple Fe(0) complex Fe­(Et₂PCH₂CH₂PEt₂)₂(N₂) (<b>1</b>) is an efficient catalyst for the selective conversion of N₂ (>25 molecules N₂ fixed) into N₂H₄, attendant with the production of ca. one molecule of NH₃. Notably, the reductant (CoCp*₂) and acid (Ph₂NH₂OTf) used are considerably weaker than conventional chemical H⁺ and e^– sources used in previous demonstrations of N₂ turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N₂ to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH₃ formation by such systems may proceed via Fe–N₂H₄ intermediates

Selective Catalytic Reduction of N₂ to N₂H₄ by a Simple Fe Complex

The catalytic fixation of N₂ by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for N₂H₄ production. Herein we report that the simple Fe(0) complex Fe­(Et₂PCH₂CH₂PEt₂)₂(N₂) (<b>1</b>) is an efficient catalyst for the selective conversion of N₂ (>25 molecules N₂ fixed) into N₂H₄, attendant with the production of ca. one molecule of NH₃. Notably, the reductant (CoCp*₂) and acid (Ph₂NH₂OTf) used are considerably weaker than conventional chemical H⁺ and e^– sources used in previous demonstrations of N₂ turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N₂ to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH₃ formation by such systems may proceed via Fe–N₂H₄ intermediates

Selective Catalytic Reduction of N₂ to N₂H₄ by a Simple Fe Complex

The catalytic fixation of N₂ by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for N₂H₄ production. Herein we report that the simple Fe(0) complex Fe­(Et₂PCH₂CH₂PEt₂)₂(N₂) (<b>1</b>) is an efficient catalyst for the selective conversion of N₂ (>25 molecules N₂ fixed) into N₂H₄, attendant with the production of ca. one molecule of NH₃. Notably, the reductant (CoCp*₂) and acid (Ph₂NH₂OTf) used are considerably weaker than conventional chemical H⁺ and e^– sources used in previous demonstrations of N₂ turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N₂ to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH₃ formation by such systems may proceed via Fe–N₂H₄ intermediates

Selective Catalytic Reduction of N₂ to N₂H₄ by a Simple Fe Complex

The catalytic fixation of N₂ by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for N₂H₄ production. Herein we report that the simple Fe(0) complex Fe­(Et₂PCH₂CH₂PEt₂)₂(N₂) (<b>1</b>) is an efficient catalyst for the selective conversion of N₂ (>25 molecules N₂ fixed) into N₂H₄, attendant with the production of ca. one molecule of NH₃. Notably, the reductant (CoCp*₂) and acid (Ph₂NH₂OTf) used are considerably weaker than conventional chemical H⁺ and e^– sources used in previous demonstrations of N₂ turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N₂ to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH₃ formation by such systems may proceed via Fe–N₂H₄ intermediates

An Electrochemical Study of Frustrated Lewis Pairs: A Metal-Free Route to Hydrogen Oxidation

Frustrated Lewis pairs have found many applications in the heterolytic activation of H₂ and subsequent hydrogenation of small molecules through delivery of the resulting proton and hydride equivalents. Herein, we describe how H₂ can be preactivated using classical frustrated Lewis pair chemistry and combined with in situ nonaqueous electrochemical oxidation of the resulting borohydride. Our approach allows hydrogen to be cleanly converted into two protons and two electrons in situ, and reduces the potential (the required energetic driving force) for nonaqueous H₂ oxidation by 610 mV (117.7 kJ mol^–1). This significant energy reduction opens routes to the development of nonaqueous hydrogen energy technology

Supporting Information from Hydrogen activation using a novel tribenzyltin Lewis acid

Characterising dat