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The importance of electron deficient Tp ligands motivates the introduction of electron-withdrawing substituents into the scorpionate framework. Since perfluorophenyltris(pyrazol-1-yl)borate affects significant anodic shifts in half-cell potentials in their metal complexes relative those of phenyltris(pyrazol-1-yl)borate analogues, the tuning opportunities achieved using 3,4,5-trifluorophenyl- and 3,5-bis(trifluoromethyl)phenyl(pyrazol-1-yl)borates were explored. Bis(amino)boranes ((3,4,5-F)C 6 H 2 )B(NMe 2 ) 2 and ((3,5-CF 3 )C 6 H 3 )B(NMe 2 ) 2 are precursors to fluorinated tris(pyrazol-1-yl)phenylborates. Thallium salts of these scorpionates exhibit bridging asymmetric κ 3 - N , N , N coordination modes consistent with the reduced π-basicity of the fluorinated phenyl substituents relative those of other structurally characterized tris(pyrazol-1-yl)phenylborates. While a comparative analysis of the spectral and X-ray crystallographic data for classical Mo(0), Mo( ii ), Mn( i ), Fe( ii ) and Cu( ii ) complexes of [((3,4,5-F)C 6 H 2 )Bpz 3 ] − and [((3,5-CF 3 )C 6 H 3 )Bpz 3 ] − could not differentiate these ligands with respect to their metal-based electronic impacts, cyclic voltammetry suggests that 3,4,5-trifluorophenyl- and 3,5-bis(trifluoromethyl)phenyl(pyrazol-1-yl)borates affect similar anodic shifts within their metal complexes, with coordination of [((3,5-CF 3 )C 6 H 3 )Bpz 3 ] − rendering metal centers more difficult to oxidize, and sometimes even more difficult to oxidize than their [C 6 F 5 Bpz 3 ] − analogues. These data suggest that the extent of phenyl substituent fluorination necessary to minimize metal center electron-richness in phenyltris(pyrazol-1-yl)borate complexes cannot be confidently predicted.more » « less
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For many who passed through his classroom, Richard Andersen demonstrated how inorganic chemistry can be taught by incorporating the research literature. The Interactive Online Network of Inorganic Chemists (IONiC) through its website and summer workshops for faculty has supported the development and sharing of more than a hundred exercises or “learning objects” derived from articles highlighting research across the inorganic field. Faculty can adapt and implement these learning objects in their own classrooms to achieve goals such as demonstrating historical context, teaching course material via current research, and elaborating on the scientific process. Literature discussion learning objects highlight current and past research in inorganic chemistry and teach students both chemistry content and how the body of inorganic knowledge is constructed.more » « less
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