Inorganic Chemistry Commons^™

Reactions Of First-Row Transition Metal Complexes In Bis(Alkoxide) Ligand Environments With Diazoalkanes: Formation Of Carbenes Versus Reductive Coupling To Form Bridging Tetrazenes, Amanda Grass

Wayne State University Dissertations

This dissertation focuses on the design and reactions of novel late transition metal carbene complexes featuring alkoxide ligand environments. The high-valent cobalt carbene Co(OR)2(=CPh2) (OR = OCtBu2Ph), featuring short Co=C bond of 1.773(3) Å, was previously reported from the reaction of Co(OR)2(THF)2 with diphenyldiazoalkane. Magnetic and spectroscopic (EPR) studies demonstrated Co(OR)2(=CPh2) to be a low-spin S = ½ complex. Computational studies, in agreement with experimental data, suggested that the electronic structure of Co(OR)2(=CPh2) lies between intermediate spin Co(III) anti-ferromagnetically coupled to a carbene radical and a Co(IV) alkylidene. This dissertation began with investigation of this complex in carbene transfer reactivity. …

Synthesis And Characterization Of Pyridine Dipyrrolide Iron Complexes Relevant To Nitrene And Carbene Group Transfer, Brett M. Hakey

Graduate Theses, Dissertations, and Problem Reports

The synthesis and electronic structures of the square-planar high-spin Fe^II complexes (^MesPDP^Ph)Fe(OEt₂) and (^MesPDP^Ph)Fe(thf) were investigated. Analysis of these compounds using a combination of ¹H NMR and ⁵⁷Fe Mössbauer spectroscopies, in conjunction with computational analysis, has resulted in a rationalization for their unusual electronic structures, which arise from the unique coordination environment enforced by the pyridine dipyrrolide chelate ligand.

The reactivity of (^MesPDP^Ph)Fe(thf) with organic azides has been probed and resulted in the isolation of an array of products that are consistent with …