A Stable Crystalline Copper(I)–N₂O Complex Stabilized as the Salt of a Weakly Coordinating Anion

Abstract

Nitrous oxide is considered a poor ligand, and therefore only a handful of well-defined metal-N O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag I ][An] ([An] =[Al(OC(CF ) ) ] ) in perfluorinated hexane leads to Cu [An], the first auxiliary ligand-free Cu salt of the perfluorinated alkoxyaluminate anion. The compound is capable of forming a stable and crystalline complex with nitrous oxide, Cu(N O)[An], where the Cu-N O bond is by far the strongest among all other molecular metal-N O complexes known. Thorough characterization of the compounds together with the crystal structure of Cu(N O)[An] complex supported with DFT calculations are presented. These give insight into the bonding in the Cu -N O system and confirm N-end coordination of the ligand.

N2O Reductase Activity of a [Cu4S] Cluster in the 4CuI Redox State Modulated by Hydrogen Bond Donors and Proton Relays in the Secondary Coordination Sphere

“…Furthermore, designing catalysts to lower this barrier is challenging because of the weak σ‐donating and π‐accepting properties of N 2 O that make it a poor ligand for most transition metals . In fact, transition‐metal complexes featuring N 2 O ligands have only been crystallographically characterized recently, in part because weakly donating ligands such as N 2 have long been known to bind competitively with N 2 O in classic complexes such as [Ru(NH 3 ) 5 L] 2+ (L=N 2 O or N 2 ) . Thus, fundamental knowledge about how transition‐metal active sites can be designed to bind and activate N 2 O is very valuable.…”

Lewis Acid‐Mediated One‐Electron Reduction of Nitrous Oxide

“…In non-donor solvents such as cyclohexane, Al(C 6 F 5 ) 3 exists in ad imeric form due to self-stabilization, [23] resulting in poor solubility.T he enhanced dissolution upon N 2 Oa ddition is indicative that the dimer is broken, presumablyd ue to formation of an adduct between the Lewis superacid Al(C 6 F 5 ) 3 and the very weakL ewis base N 2 O. [27] The formation of such an adduct is further supported by the 19 FNMR data. After N 2 Oa ddition, the 19 FNMR signals of the para-a nd meta-F atoms of Al(C 6 F 5 ) 3 shiftedu pfield, whereas that of the ortho-F shiftedd ownfield (Figure 3a vs. b).…”

“…Nitrous oxide is known to be av ery weak Lewis base [1,27] and ap oor ligand for metal complexes. [1] Our results suggest that activation of N 2 Ob ys trong Lewis acids holds promise in exploring its utility as an oxidant.…”

N2O Reductase Activity of a [Cu4S] Cluster in the 4CuI Redox State Modulated by Hydrogen Bond Donors and Proton Relays in the Secondary Coordination Sphere

“…Selected distances []and angles [8 8]: 2:Cu1-Cu2 2.6718(6), P1-N1 1.6824(15), P2-N1 1.680(2), P3-N2 1.6312 (15), P4-N2 1.635(2), P5-N3 1.6340-(15), P6-N3 1.634(2);P1-N1-P2 123.3(1), P3-N2-P4 117.3(1), P5-N3-P6 120.0(1). 1:C u1-Cu2 2.6969(6) ,Cu2-Cu3 2.6690(6) ,Cu3-Cu4 3.0175 (7) ,Cu1-Cu4 3.542(1).…”

“…[3] Furthermore,d esigning catalysts to lower this barrier is challenging because of the weak s-donating and p-accepting properties of N 2 Ot hat make it apoor ligand for most transition metals. [4,5] In fact, transition-metal complexes featuring N 2 Ol igands have only been crystallographically characterized recently, [6][7][8][9] in part because weakly donating ligands such as N 2 have long been known to bind competitively with N 2 Oi nc lassic complexes such as [Ru(NH 3 ) 5 L] 2+ (L = N 2 OorN 2 ). [10] Thus,fundamental knowledge about how transition-metal active sites can be designed to bind and activate N 2 Oi svery valuable.…”