The Clusters of Nitrogenase:  Synthetic Methodology in the Construction of Weak-Field Clusters

VFe3S4 Single and Double Cubane Clusters: Synthesis, Structures, and Dependence of Redox Potentials and Electron Distribution on Ligation and Heterometal

“…The molybdenum clusters are more susceptible to oxidation, an effect that operates in higher nuclearity clusters as well. Two practical consequences are the extremely facile oxidation of the all-ferrous EBDCs [(Tp) 2 This investigation provides basic information on accessible core oxidation states, redox stability, and electron distribution as a function of terminal ligation and heterometal in vanadium and molybdenum cubane-type clusters. Cognizance of these properties, both absolute and relative, will continue to be of consequence in the synthetic manipulation of cubane clusters directed toward new structures and their reactivity.…”

“…5-7 The clusters of interest in this context are of two types: single cubanes (SC) 8 containing the [MFe 3 (μ 3 -S) 4 ] core of idealized trigonal symmetry and edge-bridged double cubanes (EBDC) with the core [M 2 Fe 6 S(μ 3 -S) 6 (μ 4 -S) 2 ] of idealized centrosymmetry. The large majority of such clusters have been prepared with M = Mo because the immediate core coordination sphere of the molybdenum atom (MoFe 3 S 3 ) is structurally closely related to that in the nitrogenase MoFe protein.…”

Tiara-like Octanuclear Palladium(II) and Platinum(II) Thiolates and Their Inclusion Complexes with Dihalo- or Iodoalkanes

“…Metal thiolates are an important class of compounds because of their structural diversity in coordination chemistry, [1][2][3] relevance to cofactors of metalloproteins in biological systems, [4][5] and importance in cluster and surface science [6][7] and catalysis. 8 Thiolate-bridged polynuclear group 10 transition-metal complexes with chain structures, [M(-SR) 2 ] n (M = Ni, Pd), have been investigated in detail because they provide efficient catalysis of atom-economical organic reactions such as regioselective additions of thiols and disulfides across alkynes.…”

“…[8][9][10][11][12][13] Tiara-like complexes, which are also polynuclear group 10 transition-metal thiolates and are characterized by toroidal architectures, have been studied extensively, both in terms of their intriguing structural features and with respect to the preparation of monodisperse metal sulfide nanoparticles, 14 non-linear optical materials, 15 photoactive water-reducing catalysts, [16][17] and host-guest chemistry. 15,[18][19][20][21] Tiara-like nickel complexes have received considerable attention resulting in the preparation of complexes with a variety of ring sizes [Ni(-SR) 2 ] n (n = [4][5][6][8][9][10][11][12]. 15,[17][18][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] In contrast, although several tiara-like hexanuclear palladium complexes have been reported, 9,14,…”

Combining a Nitrogenase Scaffold and a Synthetic Compound into an Artificial Enzyme

“…[23][24][25][26] Such a quest began even before the structures of the nitrogenase clusters were known, when a variety of relatively small FeS clusters, including cubane-type FeS clusters with various ligands (and, in some cases, heterometals), were synthesized and characterized. [15,23] As chemical and spectroscopic information of the nitrogenase clusters became available, much effort has been focused on generation of high-nuclearity metalloclusters.…”