Brookes, Nigel JAriafard, AlirezaStranger, RobertYates, Brian F2015-12-100947-6539http://hdl.handle.net/1885/60040The experimentally known reduction of carbon monoxide using a 3-coordinate [Ta(silox)3] (silox = OSi-(tBu)3) complex initially forms a ketenylidene [(silox)3Ta-CCO], followed by a dicarbide [(silox)3Ta-CC-Ta-(silox)3] structure. The mechanism for this intricate reaction has finally been revealed by using density functional theory, and importantly a likely structure for the previously unknown intermediate [(silox)3Ta-CO]2 has been identified. The analysis of the reaction pathway and the numerous intermediates has also uncovered an interesting pattern that results in CO cleavage, that being scission from a structure of the general form [(silox)3Ta-C nO] in which n is even. When n is odd, cleavage cannot occur. The mechanism has been extended to consider the effect of altering both the metal species and the ligand environment. Specifically, we predict that introducing electron-rich metals to the right of Ta in the periodic table to create mixed-metal dinuclear intermediates shows great promise, as does the ligand environment of the Cummins-style 3-coordinate amide structure. This latter environment has the added complexity of improved electron donation from amide rotation that can significantly increase the reaction exothermicity.Keywords: Amide structures; C-O cleavage; Density-functional calculations; Dinuclear; Electron donation; Electron-rich; Metal species; Periodic table; Reaction exothermicity; Reaction mechanism; Reaction mechanisms; Reaction pathways; Amides; Carbon monoxide; Compu Carbon monoxide; Computational chemistry; Density functional calculations; Reaction mechanisms; Transition metals201010.1002/chem.2009033482016-02-24