Catalytic Reactivity of Molybdenum–Trihalide Complexes Bearing PCP‐Type Pincer Ligands

Abstract

Molybdenum–iodide complexes bearing a PCP[1] ligand have been found to work as excellent catalysts toward ammonia formation under ambient reaction conditions among dinitrogen‐bridged dimolybdenum complexes and other molybdenum complexes bearing PNP and PCP[2] ligands.

Molybdenum-Containing Metalloenzymes and Synthetic Catalysts for Conversion of Small Molecules

“…of NH 3 production per catalyst, which was 35 times higher activity than the N 2 -bridged Mo 2 complex. Furthermore, they examined the effect of PCP-type carbene ligands of 1,3-bis((di-tert-butylphosphino)methyl)benzimidazol-2-ylidene (PCP-1), 1,3-bis(2-(di-tertbutylphosphino)ethyl)imidazol-2-ylidene (PCP-2) [126] (Scheme 16). The PCP-1-Mo (33) produced 100 equiv.…”

“…Interestingly, the mutation by β-98 His improved electron-accepting ability from an un-natural reducing agent to promote reductions of azide (N 3 − ) or nitrite (NO 2 − ) to NH 3 [147]. Using electron mediators such as polyaminocarboxylate-ligated Eu [126] and polyallylamine (PAA) polymer-CoCp 2 [148] further improved reduction efficiencies. Rather in the presence of Fe-protein, without using an additional electron mediator, electron transfer between Fe-protein and FeMocluster became slow.…”

Nitrogen Fixation Catalyzed by Dinitrogen‐Bridged Dimolybdenum Complexes Bearing PCP‐ and PNP‐Type Pincer Ligands: A Shortcut Pathway Deduced from Free Energy Profiles

“…[8] Their Mo- fixation. At present, a molybdenum trihalide complex is known as the most effective metal complex that catalyzes nitrogen fixation under ambient conditions, [9] while titanium-, [10] vanadium-, [11] iron-, [12][13][14][15][16][17][18][19] molybdenum-, [20][21][22][23][24][25][26] ruthenium-, [27] osmium-, [27] and cobalt-catalyzed [28] direct transformations of dinitrogen into ammonia and hydrazine have been achieved by recent intensive experimental works in this field of research.…”

“…All rights reserved ] exhibited significantly high catalytic activity. [9,24,25] In order to explain the high catalytic performance, the dimolybdenum Mo(I)Mo(I)-halide species [MoX-N≡N-MoX] (X = halide) is considered to be a key intermediate that enables the direct N≡N bond cleavage. We believe that synergetic experimental and computational investigations on the reactivity of dinitrogen-bridged dimolybdenum complexes will open a new way to the development of more effective catalysts for nitrogen fixation working under ambient reaction conditions.…”

Chlorination‐Promoted Cage Transformation of IPR C92 Discovered via Trifluoromethylation under Formation of Non‐classical C92(NC)(CF3)22

“…An X-ray diffractionstudy with the use of synchrotron radiation revealed the known structure of C 92 (81/82)CF 3 ) 16 and new structures of IPR C 92 (38)(CF 3 ) 18 and non-classical C 92 (NC)(CF 3 ) 22 . [12] The molecules of new CF 3 derivativeso fC 92 isomersa re shown in Figure1 in two projectionse ach. The molecule of C 92 (38)(CF 3 ) 18 represents the highly trifluoromethylated CF 3 derivativeo fi somer C 92 (38) whereas the compound C 92 (38)(CF 3 ) 14 and severali somerso fC 92 (38)(CF 3 ) 16 have been knownb efore.…”