Heterometallic

Heterometallic ferrocene-based transition metal compounds. P. N. Gaponik, A. I. Lesnitovich and Y. G. Orlik, Russ. Chem. Rev. (Engl. Transl), 1983,52,168-183 (293). 

Selective metal-ligand interactions in heterometallic transition metal clusters. E. Sappa, A. Tiripio-chio and P. Braunstein, Coord. Chem. Rev., 1985, 65, 219 (218). 

Metal AlkoxidesandDiketonates, and Double-Metal Alkoxides/ Heterometallic Alkoxides, sections in Gelest Inc. Handbook, Milwaukee, WI (1995)... 

Homometallic and Heterometallic Transition Metal Allenyl Complexes Synthesis,... 

Fig. 3. Ground state spin (S) and valence delocalization schemes for the known oxidation states of [Fe3S4] clusters. Discrete [Fe3S4] clusters have not been observed in siny protein, but they have been identified as fragments in heterometallic cubane clusters. Reduction of the [Fe3S4]+ cluster by three electrons, to yield a putative aU-ferrous cluster, occurs with the concomitant addition of three protons. Key S , grey Fe +, black Fe +, white Fe, white with central black dot.

For heterometallic clusters with [Fe3S4] couples, the order potentials can be summarized as follows ... 

These studies of protein-bound heterometallic cubanes have amply demonstrated that the heterometal site is redox active and able to bind small molecules. Although they have yet to be identified as intrinsic components of any protein or enzyme (except as part of the nitrogenase FeMo cofactor cluster (254)), they are clearly attractive candidates for the active sites of redox enzymes. 

In contrast to the abundance of Fe-proteins, there are only six known nickel-containing enzymes hydrogenase, CO dehydrogenase (CODA), acetyl-CoA synthase (ACS), superoxide dismutase, urease, and S-methyl-CoM methylreductase. Among these enzymes, it exists in very diverse environments, including a dinickel site (urease), a Ni-Fe heterobinuclear site (hydrogenase), a Ni-Fe4S4 heterometallic... 

CODH from acetogens found to catalyze acetyl-CoA synthesis and nickel proposed to be the active site of CO oxidation and acetyl-CoA synthesis. CODH found to contain a heterometallic cluster consisting of nickel and iron that binds CO and proposed to be the active site of acetyl-CoA synthesis. Growth of acetogens on nitrate disables the acetyl-CoA pathway. ... 

Trinuclear Cuboidal and Heterometallic Cubane-Type Iron-Sulfur Clusters New Structural and Reacticity Themes in Chemistry and Biology R. H. Holm... 

Ligand activation and transformation at heterometallic clusters have been reviewed, but few examples of very mixed -metal clusters effecting these... 

Very few reports concerning transformations of ligands with other donor atoms exist (Table V). P—H activation at secondary phosphines is the most common motif, with the metal-metal bonds at the heterometallic faces stabilizing the resulting fragments in each case (Figs. 31. 32, 33).In the formation of both... 

Reactions of clusters with mononuclear or dinuclear metal complexes frequently provide a method of expanding the metal core nuclearity under controlled conditions. The majority of medium- and high-nuclearity homometallic clusters has been prepared from lower-nuclearity cluster precursors by thermolyses ("heat-it-and-hope ) reactions. This is less true of the heterometallic clusters in this... 

The electrochemical behavior of heterometallic clusters has been reviewed clsewbcre."" The interest in examining clusters stems from their potential to act as "electron sinks " in principle, an aggregate of several metal atoms may be capable of multiple redox state changes. The incorporation of heterometals provides the opportunity to tune the electrochemical response, effects which should be maximized in very mixed"-metal clusters. Few very mixed -metal clusters have been subjected to detailed electrochemical studies the majority of reports deal with cyclic voltammetry only. Table XII contains a summary of electrochemical investigations of "very mixed"-metal clusters. 

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