HIGH OXIDATION STATE TRANSITION METAL CHEMISTRY

点击翻译按钮获取中文摘要

The long-term objective of this research is to determine how molecular nitrogen can be reduced to ammonia catalytically under ambient conditions employing a well-defined transition metal complex, protons, and electrons. The short-term objective is to investigate the chemistry of relatively high oxidation state complexes of (primarily) Mo or W that contain trianionic triamido/donor and related ligands, especially chemistry that is relevant to the reduction of dinitrogen, including the chemistry of complexes that contain N2Hx (x = 0.4) or NHy (Y = 0-3) ligands. We wish to determine what principles are of fundamental and general significance to the reduction of dinitrogen to ammonia. In the process we also want to remain open to the possibility of "fixing" dinitrogen in the form of some nitrogen..containing organic molecule, at first stoichiometrically, and ultimately catalytically. Specifically, we first want to prepare and study complexes that contain Mo or W and known triamidoamine ligands, [(RNCH2CH2)3N]3- (R = trialkylsilyl, C6F5). We then want to prepare potentially more stable variations in which R is (e.g.) CH(CF3)2 or C(C6H5)(CF3)2. Analogous ligand systems that contain P or As donors in place of N will also be prepared and attached to Mo and W in order to address the issue of apical donor ligand binding. Other variations will also be explored, including tridentate trianionic ligands such as ([RNC(SiMe3)2]3CR')3- and tribenzimidazolatoamine ligands. Finally we want to synthesize related complexes in which dinitrogen could be bound and reduced within a "cage" or "cavity," a circumstance that would eliminate the problem of bimolecular decomposition of intermediates in the dinitrogen reduction process by inorganic complexes in solution.