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- W61971029 abstract "Rationally designed transition metal complexes can be used to “activate” O2— that is, to transform it into a highly reactive oxidant capable of activating C–H bonds. The reactive species generated in this reaction sequence is a bis(μ-oxo) complex, resulting from cleavage of the O–O bond of a dioxygen ligand. The resulting M2(μ-O)2 diamond core structure is emerging as a common structural feature in late transition metal dioxygen chemistry— that is, for Mn, Fe, Co, and Cu. The “activation of dioxygen,” that is, its transformation into a highly reactive, and yet selective reagent for the oxidation of a wide range of organic substrates, is, thus, a major challenge for research in catalysis. This chapter describes the efforts to design metal complexes for this ultimate purpose. The study described in this chapter is looking for a ligand to occupy the remaining three coordination sites of a tetrahedron, while at the same time preventing the formation of complexes with higher coordination numbers. Tris(pyrazolyl)borate ligands with bulky substituents in the 3-position of the pyrazole rings, so called “tetrahedral enforcers,” seemed an attractive choice. This class of ligands are well-flexible in tuning the steric requirements of the remaining fourth coordination site; their monoanionic nature compensates some positive charge of high-valent metal ions and combined with the lipophilic character of the ligand solubility of the complexes in nonpolar organic solvents might be expected. The particular ligands used in this work were Tpt-Bu,Me and Tpi-Pr,Me." @default.
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- W61971029 date "1997-01-01" @default.
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- W61971029 title "Dioxygen activation with sterically hindered tris(pyrazolyl)borate cobalt complexes" @default.
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- W61971029 doi "https://doi.org/10.1016/s0167-2991(97)81074-9" @default.
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