Hydrogenases biomimetic models

Dithiocarbamates, in Ru and Os half-sandwiches, 6, 493 Dithiocarbenes, Pt complexes, 8, 439 Dithiocarboxy ligands, in molybdenum carbonyls, 5, 447 Dithiolate-bridged compounds in dinuclear iron compounds with Fe-Fe bonds, 6, 238 as iron-only hydrogenase biomimetic models, 6, 239 Dithiolate diamides, with Zr(IV), 4, 784 Dithiolene—uranium complexes, synthesis and characterization, 4, 212 Ditopic receptors, characteristics, 12, 489 Ditungsten complexes, associated reactions, 5, 748 Divinyllead diacetates... 

Beer PD, Bayly SR (2005) Anion Sensing by Metal-Based Receptors. 255 125-162 Bertini L, Bruschi M, de Gioia L, Fantucci P, Greco C, Zampella G (2007) Quantum Chemical Investigations of Reaction Paths of Metalloenzymes and Biomimetic Models - The Hydrogenase Example. 268 1-46 Bier FF, see Heise C (2005) 261 1-25... 

Ma Y, Balbuena PB (2007) Density functional theory approach for improving the catalytic activity of a biomimetic model based on the Fe-only hydrogenase active site. J Electroanal Chem (in press)... 

Iron-only hydrogenase, dithiolate-bridged compounds as biomimetic models, 6, 239 Iron oxide films, synthesis, 12, 51 Iron-palladium nanoparticles, preparation, 12, 74 Iron-platinum bimetallic clusters, with isocyanide clustes,... 

The work on biomimetic models for [NiFe] and [FeFe] hydrogenase has been described in several review articles [15b 158]. In this work, many of the structural features important for proper function found in the native systems have been successfully incorporated for example, the bimetallic Ni-Fe or Fe-Fe core with rather short metal-metal distances and an open coordination site at one metal, the sulfur-rich environment (terminal and bridging thiolate ligands), CO/CN ligation of the iron(s), and the incorporation of a base for acceptance of the proton and, more recently, of hydride bridges. Still-existing problems of many model systems are the O2 sensitivity, the high overpotentials, and lack of activity (low turnover rates). 

Roy S, Groy TL, Jones AK (2013) Biomimetic model for [FeFe]-hydrogenase asymmetrically disubstituted diiron complex with a redox-active 2,2 -bipyridyl ligand. Dalton Trans 42 (ll) 3843-3853. doi 10.1039/c2dt32457a... 

Lansing JC, Camara JM, Gray DE, Rauchfuss TB (2014) Hydrogen production catalyzed by bidirectional, biomimetic models of the [FeFej-hydrogenase active site. Organometallics 33 (20) 5897-5906. doi 10.1021/om5004013... 

Following the first syntheses of biomimetic models of the [FeFe]-hydrogenase active site covalently linked to a ruthenium photosensitizer by Akermark, Sun, and their coworkers in 2003 [90,91], various diiron dithiolate mimics have been combined to a photosensitizing unit [92-100]. 

Dithiolate-bridged Compounds as Biomimetic Models for Iron-only Hydrogenase Selenolate and Tellurolate-bridged Compounds Bis(acyl)-bridged Compounds... 

Dithiolate-bridged Compounds as Biomimetic Models for Iron-only Hydrogenase... 

Ott, S. Kritikos, M. Akermark, B. Sun, L. C. Synthesis and structure of a biomimetic model of the iron hydrogenase active site covalently linked to a ruthenimn photosensitizer. Angew. Chem. Int. Ed. 2003, 42, 3285-3288. 

Biomimetic chemistry of nickel was extensively reviewed.1847,1848 Elaborate complexes have been developed in order to model structural and spectroscopic properties as well as the catalytic function of the biological sites. Biomimetic systems for urease are described in Section 6.3.4.12.7, and model systems for [Ni,Fe]-hydrogenases are collected in Section 6.3.4.12.5. 

Biomimetic Efficiency A Structural and Electronic Investigation of Rotational Barriers Found in DFT-inspired Fe-hydrogenase Models... 

Production of H2 fuel from water via solar energy is of exceedingly high interest.115 Catalysis may involve H2 complexes at least as intermediates, and H2 complexes had previously been implicated in solar energy conversion schemes based on photoreduction of water.116 Industrially important water-gas shift and related H2-producing reactions undoubtedly proceed via transient H2 complexes.117 Biomimetic H2 production, particularly solar driven (via photocatalysis), is also a challenge and may take a cue from models of the active site of hydrogenase coupled with models of nature s photosystems.91-93 Here, the formation of H-H bonds from protons and... 

Light-driven acceptor side (H2 formation) assemblies employ both biomimetic catalysts modeled after the hydrogenase active site (Fe, Ni complexes) as well as other catalysts based on abundant metals like cobalt but with non-biomimetic structures. The catalyst shown in Fig. le is an example of an iron-iron [FeFe] hydrogenase active site model that has been employed in a system for photocatalytic... 

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