Copper sulfide clusters

The P4 molecule also reacts with the copper sulfide cluster anions generally giving products involving addition of P2 and in some cases the addition of a further P2 unit (257). Only Cu6S4 was unreactive toward P4 and even [Cu3S3p reacted, albeit slowly, to produce the P2 adduct. The CID studies of Cu2S2P2 (XIV) yielded P2S, and [Cu2S3P2p XV yielded P2S and PS2, consistent with calculated structures that showed insertion of P2 into the Cu-S bonds as shown in XIV and XV. 

The reactions of P4 with the metal sulfide cluster anions has been extended to Ni, Co, and Fe (99). The copper sulfide cluster anions were generally the least reactive anions toward P4 with similar anions having reactivities [NinSJ > [Co SA ... 

Lack of reactivity in copper sulfide cluster anions has been associated with structural features such as linear S-Cu-S bonding. Reactivity of metal sulfide cluster anions is associated with exposed under-coordinated metal atoms able to bond to coordinating molecules this is the essence of this chapter. 

The biological significance of these reactions is considered further in Chapters 18 and 24. The 132-kDa dimeric N20 reductase from Pseudomonas stiltzeri contains four copper atoms per subunit.546 One of its copper centers resembles the CuA centers of cytochrome c oxidase. A second copper center consists of four copper ions, held by seven histidine side chains in a roughly tetrahedral array around one sulfide (S2 ) ion. Rasmussen et al. speculate that this copper-sulfide cluster may be an acceptor of the oxygen atoms of N20 in the formation of N2.546a There is also a cytochrome cdj type of nitrite reductase.1433... 

Copper-sulfide cluster 884s Coproporphyrin III 843,845s Comified cell envelope 439 Corrin in transmethylation 592 Corrin ring 867, 868 Corrinoid-dependent synthesis of acetyl-CoA 876, 877 Cosmarium 22 COSY-NOESY diagram 143 Cotransport (symport) process 411,416,417 Coulomb 283... 

In the molecular structure of 8, the start of the transition is observed, from the so-called small copper sulfide clusters to the middle-sized species. Both cluster sizes possess spherical Cu S—P frameworks with copper centers near the Sn polyhedral edges, but the middle-sized examples show some new structural features coordination numbers other than four for sulfur atoms, and copper centers that bind to more than two sulfur neighbors. 

Table 9 Copper sulfide clusters synthesized using silylated chalcogen reagents.

In a series of papers, metal sulfide cluster anions of first-row transition metals, principally copper, have been reacted with a variety of reagents including thiols, sulfur, phosphorus, and phosphines (99, 145, 256, 257). 

Theberge SM, Luther GW, Rozan TF, Rickard DT (2000) Evidence for aqueous clusters as intermediates during copper sulfide formation. Abstr Am Chem Soc 220 353 Thompson DN, Sayer RL, Noah KS (2000) Sawdust-supported passive bioremediation of western United States acid rock drainage in engineered wetland systems. Minerals Metall Process 17 96-104 Tolman RC (1966) Consideration of Gibbs theory of surface tension. J Chem Phys 16 758-774 Tolman RC (1949) The effect of droplet size on surface tension. J Chem Phys 17 333-337 Tomino H, Kusaka I, Nishioka K, Takai T (1991) Interfacial tension for small nuclei in binary nucleatioa J Crystal Growth 113 633-636... 

The crystals that are obtained from the cluster formation reactions are intensely colored. In fact, the intensity of the color increases when going from sulfur- to selenium- to tellurium-bridged compounds (see below), as might be expected for an increase in the covalent or (semi-) metallic binding properties. Small copper sulfide and selenide clusters form light red, orange, or purple crystals, but with increasing cluster size the color varies from dark red to reddish-black to (finally) black with a metallic sheen. The optical spectra of some copper selenide cluster compounds have been studied by means of solid-state UV-visible spectroscopy. 

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