Synthesis, structures, and reactivity of biologically relevant sulfur-containing copper(i) complexes

Several aspects of the bioinorganic chemistry of copper remain elusive. Low-coordinate, sulfur-containing copper sites appear to play different, yet very important roles in biology. These motifs are not well understood, but are implicated in biological copper sequestration, copper transfer, and are found as part of an active site within a particular metalloenzyme system that catalyzes water-gas shift chemistry. The work described in this dissertation details the exploratory synthesis aimed at modeling these systems.;Synthetic efforts to gain access to two-coordinate copper(I) bis(thiolato) species which model copper metallochaperones and metalloregulatory proteins are outlined in Chapter 1. To this end, the synthetic preparation of a new, bulky thiolate ligand precursor, 1-(thioacetyl)triptycene, was devised. Upon deprotection to form 1-(thiolato)triptycene, this ligand affords several new low-coordinate cuprous thiolate complexes. One particular species, [Bu 4N][Cu(STrip)2], exists as an analogue of the copper metallochaperones and metalloregulatory proteins described previously. A cyclic hexameric species, [Bu4N][(CuSTrip)6(mu6-Br)], emerged from the coordination chemistry and features a new cuprous thiolate structure type. Additionally, a few organometallic copper(I) complexes bearing the triptycene ligand are discussed.;Chapter 2 describes the synthesis of new, potentially useful two- and four-coordinate copper(I) silylthiolate complexes and cuprous metallothiols. Here, synthesis and characterization of [Cu(IPr)(SH)] represents the first example of a two-coordinate copper metallothiol species is reported. The reactivity of both copper(I) silylthiolates and cuprous metallothiols was explored within the context of their potential use as starting materials in an effort to construct heteronuclear species.;Chapter 3 details the synthetic efforts toward assembling a structural analogue of the metalloenzyme active site of molybdenum-dependent carbon monoxide dehydrogenase (Mo-CODH). Two synthetic methodologies, silane-mediated coupling and the reaction of terminal sulfido molybdenum species with labile copper(I) salts, were explored in this context. Several new heteronuclear cluster species containing [Mo(mu-S)2Cu] rhomb core units were formed from the reactions outlined in this chapter. Conclusions are discussed with regard to the synthetic nuances associated with generating a synthetic analogue of the active site of Mo-CODH.;Multinuclear copper species bearing diamino-dithiolate (N2S 2) ligands which formed either serendipitously via ligand exchange or by deliberate syntheses are described in Chapter 4. Copper complexes containing N2S2 ligands appear to stabilize or support mixed-valence cores and can access a variety of structure types. The interesting features associated with these structures are discussed and comments regarding the potential reactivity of these species are framed within a bioinorganic context.