Developments in the Biomimetic Chemistry of Cubane-Type and Higher Nuclearity Iron–Sulfur Clusters

Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane

“…Detailed spectroscopic analysis of the substrates coordinated to the cluster framework has provided unique insight into the function of the active surface in, for example, the chemisorption process [4,5]. Moreover, some of the clusters provide structural and/or functional mimics of the active sites in enzymes [6][7][8][9]. A typical way to prepare the clusters is the self-assembly of metals and bridging ligands, by simply mixing the appropriate metal precursors in proper molar ratios under suitable reaction conditions.…”

Cs[FeSe2], Cs3[FeSe2]2, and Cs7[Fe4Se8]: Missing Links of Known Chalcogenido Ferrate Series

“…A similar relationship is widely documented for the S 2-/-SH/-SR ferrates. [48,17] In the crystal structure of Cs 7 [Fe 4 Se 8 ] the μ 3 -bridging Se(1) and Se(2) atoms are -additional to the three iron ions -coordinated by six Cs cations at distances between 358.8 and 455.1 pm resulting in an overall 3 + 6 coordination ( Table 4). The six Cs cations are arranged in a flattened trigonal-prismatic shape around the pseudo threefold axis of the cluster.…”

“…Figure 7) Here, each such column shares common faces with four neighboring columns only, which are all shifted 1/2 of the cube height. [19] The arrangement of the [Fe 4 Q 4 ] n+ cubane-type clusters in natural and biomimetic model compounds has been extensively studied by Holm et al [48][49][50] In these studies, the volume of the [Fe 4 Q 4 ] "stella quadrangular" cluster is calculated by summing up the volume of the inner [Fe 4 ] tetrahedron (red in Figure 7) and the four [Fe 3 Q] tetrahedra (blue). Table 5 summarizes the respective volumes and selected intra-cluster distances of the known alkali salts containing cubane-type clusters.…”

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

“…[1][2][3][4][5][6][7] Among these reactions, the reduction of N 2 to ammonia (NH 3 ) represents a key step in the global nitrogen cycle; whereas the conversion of CN − , CO and CO 2 to hydrocarbons provides an important template for future development of strategies to recycle carbon wastes into useful carbon fuels. [8,9] The "conventional" molybdenum (Mo)-nitrogenase consists of two component proteins: a γ 2 -dimeric reductase (designated NifH), which houses a subunit-bridging [Fe 4 S 4 ] cluster and an ATP-binding site within each subunit; and a α 2 β 2 -tetrameric catalytic component (designated NifDK), which contains a Pcluster ([Fe 8 S 7 ]) at the α/β-subunit interface and an M-cluster ([(Cit)MoFe 7 S 9 C]; Cit, homocitrate) within each α-subunit ( Figure S1A).…”

“…[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.…”