Formation, Reactivity, and Properties of Nondative Late Transition Metal−Oxygen and −Nitrogen Bonds

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Abstract
Complexes containing bonds between heteroatoms such as nitrogen and oxygen and “late” transition metals (i.e., those located on the right side of the transition series) have been implicated as reactive intermediates in numerous important catalytic systems. Despite this, our understanding of such M−X linkages still lags behind that of their M−H and M−C analogues. New synthetic strategies have now made possible the isolation and study of a variety of monomeric late-metal alkoxide, aryloxide, and amide complexes, including parent hydroxide and amide species. The heteroatoms in these materials form surprisingly strong bonds to their metal centers, and their bond energies do not necessarily correlate with the energies of the corresponding H−X bonds. The M−X complexes typically exhibit nucleophilic reactivity, in some cases form strong hydrogen bonds to proton donors, and even deprotonate relatively weak acids. These observations, as well as thermodynamic investigations, suggest that late metal−heteroatom bonds are strongly polarized and possess significant ionic character, properties that play an important role in their interactions with organic compounds.

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