Mankad, Neal P. (2010) Copper and iron complexes with unusual coordination geometries enforced by phosphine chelates. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:03112010-172248190
Chelating phosphine ligands were used to enforce targeted coordination geometries onto complexes of iron and copper, thereby imparting molecular properties distinct relative to species studied previously in other geometries. The bulky bis(phosphino)borate ligand [Ph_2B(CH_2P^tBu_2)_2]^- was used to provide trigonal planar complexes of Cu. This structural motif provided a rare opportunity for a single framework to stabilize Cu complexes in three discrete oxidation levels and allowed for the study of unique ligands including diazoalkanes, a diphenylcarbene, diarylamides, and a diarylaminyl radical. In the latter case, physical measurements (multiedge XAS and multifrequency EPR spectroscopy) and theoretical methods (DFT) were used to quantitate the delocalization of spin density between the Cu center and the NAr_2 unit, providing a comprehensive electronic structure picture for L_2CuER_2 (E = C or N) complexes in this system. In separate studies, trigonal bipyramidal Fe complexes were generated using the bulky, anionic tris(phosphino)silyl ligands [(2-R_2PC_6H_4)_3Si]^- (R = Ph or iPr). Low-valent Fe species in this system were found to activate dinitrogen, providing labile N_2 ligands trans to the silyl donor, including the first instance of a terminally bound N_2 ligated to a paramagnetic Fe center. Subsequent reactions involving these Fe^I-N_2 species and organoazides provided entry to unusual catalytic N-N coupling reactions. These reactions were found to involve reactive FeNAr intermediates, destabilized by virtue of the trigonal bipyramidal coordination geometry, which subsequently coupled bimolecularly in the N-N bond-forming step. The effects of perturbing previously studied C_3-symmetric pseudotetrahedral iron complexes to their trigonal bipyramidal analogues proved key to uncovering the chemistry of interest.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Subject Keywords:||Copper, Iron, Phosphine, Diazoalkane, Carbene, Redox, Non-innocent, Radical, Ligand, Dinitrogen fixation, Organoazide, Nitrene, Imido|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||4 December 2009|
|Author Email:||nealm (AT) caltech.edu|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Neal Mankad|
|Deposited On:||19 Mar 2010 17:01|
|Last Modified:||26 Dec 2012 03:22|
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