Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Abstract

Incorporation of monatomic 2p ligands into the core of iron-sulfur clusters has been researched since the discovery of interstitial carbide in the FeMo cofactor of Mo-dependent nitrogenase,but has proven to be asynthetic challenge.Herein, two distinct synthetic pathwaysa re rationalized to install nitride ligands into targeted positions of W-Fe-S clusters, generating unprecedented nitride-ligated iron-sulfur clusters, namely [(Tp*) 2 W 2 Fe 6 (m 4 -N) 2 S 6 L 4 ] 2À (Tp* = tris(3,5-dimethyl-1-pyrazolyl)hydroborate(1À), L = Cl À or Br À ). 57 Fe Mçssbauer study discloses metal oxidation states of W IV 2 Fe II 4 Fe III 2 with localized electron distribution, which is analogous to the midvalent iron centres of FeMo cofactor at resting state.G ood agreement of Mçssbauer data with the empirical linear relationship for Fe-S clusters indicates similar ligand behaviour of nitride and sulfide in such clusters,p roviding useful reference for reduced nitrogen in an itrogenase-like environment.Scheme 1. Distinct synthetic pathwayso fcluster 3.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cubane-type tungsten–iron–sulfur clusters with a nitrogen atom in the core: terminal ligand substitutions and redox behaviors

“…Despite years of efforts toward the analogs of nitrogenase related iron-sulfur clusters, the majority of clusters thus synthesized are homoleptic in the core to comprise sulfides as the sole type of core ligand, being quite different from the FeMo cofactor structure which comprises a core 2p atom. There were homo-or hetero-metal ironsulfur clusters incorporating 2p atom(s) in the core synthesized by the strategy of self-assembly, [7][8][9][10][11][12][13] and the rational strategy of core ligand metathesis developed by Chen et al has provided a rational way for the introduction of 2p atom(s) into the core of M-Fe-S clusters. [11][12][13] Before establishing any rational strategies to incorporate 2p atoms into the core of homo-or hetero-metal iron-sulfur clusters, heterometal cubane-type clusters with a [MFe 3 S 4 ] z (M = Mo, W or V) core have been intensively studied as close topological analogs of the partial structure of the FeMo cofactor.…”

Stepwise Construction of Mo–Fe–S Clusters Using a LEGO Strategy

“…Many synthetic iron–sulfur clusters − have been synthesized, but those with light elements (C, N, or O) ,− are rarely seen in either homometallic or heterometallic iron–sulfur clusters. A few Fe 8 S 7 clusters with N ligands as the intercubane bridges have been synthesized by self-assembly, , but installing a light atom into the core of Fe–S or M–Fe–S (M = Mo or W) clusters remains a challenge. ,,,− There were successful attempts to incorporate light atoms into the cluster core, where typical examples were a series of iron–sulfur cubane clusters with a heteroligated core featuring a core N atom using the synthetic strategy of fragment condensation, , P N -type clusters with N-containing ligands at the μ 2 -bridging sites, ,, and an iron–thiolate compound with an O atom . In our laboratory, we have recently developed controlled synthetic strategies named core ligand metathesis and core ligand redox metathesis, with which one can incorporate an N or O atom into the core of W–Fe–S clusters .…”

Construction of cluster-based supramolecular wire and rectangle

“…In the past few decades, the construction of novel Mo(W)/Cu/S clusters from reactions of metal sulfide synthons including [MO x S 4−x ] 2− (M = Mo, W, x = 0-3); [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] [Cp*MS 3 ] − (Cp* = pentamethylcyclo-pentadienyl); [17][18][19][20][21][22][23][24][25] [Tp*WS 3 ] − (Tp* = hydridotris (3,5-dimethyl-pyrazol-1-yl)borate) [26][27][28][29][30][31][32][33][34][35][36][37] with Cu(I) salts, halides and various nitrogen donor ligands has been extensively studied due to their variable structures and potential applications in the simulation of biological enzyme active centers, 38,39 optoelectronic materials, 4,40,41 catalysis 27,42,43 and sensing. 44,45 Some groups in the ...…”

“…In the past few decades, the construction of novel Mo(W)/Cu/S clusters from reactions of metal sulfide synthons including [MO x S 4− x ] 2− (M = Mo, W, x = 0–3); 1–16 [Cp*MS 3 ] − (Cp* = pentamethylcyclo-pentadienyl); 17–25 [Tp*WS 3 ] − (Tp* = hydridotris(3,5-dimethyl-pyrazol-1-yl)borate) 26–37 with Cu( i ) salts, halides and various nitrogen donor ligands has been extensively studied due to their variable structures and potential applications in the simulation of biological enzyme active centers, 38,39 optoelectronic materials, 4,40,41 catalysis 27,42,43 and sensing. 44,45 Some groups in the world have also been involved in constructing Mo(W)/Cu/S cluster-supported supramolecular compounds by assembling Mo(W)/Cu/S cluster precursors with N donor ligands like CN − , 4,4′-bipyridne (4,4′-bipy), 1,2-bis(4-pyridyl)ethane (bpea).…”