Actions for Synthesis and Exploratory Catalysis of 3d Metals [electronic resource] : Group-Transfer Reactions, and the Activation and Functionalization of Small Molecules Including Greenhouse Gases

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Synthesis and Exploratory Catalysis of 3d Metals [electronic resource] : Group-Transfer Reactions, and the Activation and Functionalization of Small Molecules Including Greenhouse Gases

Published
Washington, D.C. : United States. Dept. of Energy, 2014.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Additional Creators
University of Pennsylvania, United States. Department of Energy, United States. Department of Energy. Office of Science, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
Our work over the past three years has resulted in the development of electron rich and low-coordinate vanadium fragments, molecular nitrides of vanadium and parent imide systems of titanium, and the synthesis of phosphorus containing molecules of the 3d transition metal series. Likewise, with financial support from BES Division in DOE (DE-FG02-07ER15893), we now completed the full characterization of the first single molecular magnet (SMM) of Fe(III). We demonstrated that this monomeric form of Fe(III) has an unusual slow relaxation of the magnetization under zero applied field. To make matters more interesting, this system also undergoes a rare example of an intermediate to high-spin transition (an S = 3/2 to S = 5/2 transition). In 2010 we reported the synthesis of the first neutral and low-coordinate vanadium complexes having the terminal nitride functionality. We have now completed a full study to understand formation of the nitride ligand from the metastable azide precursor, and have also explored the reactivity of the nitride ligand in the context of incomplete and complete N-atom transfer. During the 2010-2013 period we also discovered a facile approach to assemble low-coordinate and low-valent vanadium(II) complexes and exploit their multielectron chemistry ranging from 1-3 electrons. Consequently, we can now access 3d ligand frameworks such as cyclo-P3 (and its corresponding radical anion), nitride radical anions and cations, low-coordinate vanadium oxo’s, and the first example of a vanadium thionitrosyl complex. A cis-divacant iron(IV) imido having some ligand centered radical has been also discovered, and we are in the process of elucidating its electronic structure (in particular the sign of zero field splitting and the origin of its magnitude), bonding and reactivity. We have also revisited some paramagnetic and classic metallocene compounds with S >1/2 ground states in order to understand their reactivity patterns and electronic structure. Lastly, we are completing the synthesis and characterization of a titanium nitride anion and formation of the first example of boryl and aluminyl imido titanium complexes.
Report Numbers
E 1.99:doe-upenn-er15893
doe-upenn-er15893
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Note
Published through SciTech Connect.
05/07/2014.
"doe-upenn-er15893"
Mindiola, Daniel J.
Type of Report and Period Covered Note
Final;
Funding Information
FG02-07ER15893
View MARC record | catkey: 14392117