| Metal-metal (M2) quadruply bonded complexes have a rich, diverse chemistry. From providing insight into fundamental chemistry, to having applications in materials chemistry, they continue to fuel the imagination of many inorganic chemists. Perhaps the most interesting aspect of complexes containing M 2 (M = MO, W) quadruple bonds are their physical and electronic structures. This thesis demonstrates an "aufbau" for understanding metal-metal quadruply bonded complexes. We begin by examining the spectral and electronic properties of simple paddlewheel complexes of the form M2(O2CR) 4 (M = MO, W; R = tBu-experimental; CH3, H-computational models). From there, we move to understanding the subtle electronic and thermodynamic features of more complex systems, i.e. [(HCO2) 3M2]2(mu-O2CCO2). We then move from understanding complexes of the form [(HCO2)2M 2]4(mu-O2CCO2)4 to [M 2(mu-O2CCO2)]infinity, the "infinite limit" of an extended structure. Finally, we investigate the unique chemistry of systems linked by 4,4'-azodibenzoic acid, applying what we know from similar studies of related systems. Throughout this work, computational techniques utilizing density functional theory is emphasized, as it has proven quite successful in predicting and reproducing experimental results. |
