%0 Journal Article
%A Lionetti, Davide
%A Suseno, Sandy
%A Tsui, Emily Y.
%A Lu, Luo
%A Stich, Troy A.
%A Carsch, Kurtis M.
%A Nielsen, Robert J.
%A Goddard, William A.
%A Britt, R. David
%A Agapie, Theodor
%D 2019
%T Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom
Transfer Reactivity of Heterometallic Mn3MO4 Cubane and Fe3MO(OH) and Mn3MO(OH) Clusters
%U https://acs.figshare.com/articles/journal_contribution/Effects_of_Lewis_Acidic_Metal_Ions_M_on_Oxygen-Atom_Transfer_Reactivity_of_Heterometallic_Mn_sub_3_sub_MO_sub_4_sub_Cubane_and_Fe_sub_3_sub_MO_OH_and_Mn_sub_3_sub_MO_OH_Clusters/7691906
%R 10.1021/acs.inorgchem.8b02701.s001
%2 https://acs.figshare.com/ndownloader/files/14303207
%K OAT
%K Heterometallic Mn 3 MO 4 Cubane
%K Fe 3 cores
%K Lewis acidity
%K oxygen atom transfer
%K Lewis acidic metal centers
%K group transfer reactivity
%K redox
%K Lewis Acidic Metal Ions
%K metal oxo species
%K Oxygen-Atom Transfer Reactivity
%K II
%K modulating cluster electronics
%X The
modulation of the reactivity of metal oxo species by redox
inactive metals has attracted much interest due to the observation
of redox inactive metal effects on processes involving electron transfer
both in nature (the oxygen-evolving complex of Photosystem II) and
in heterogeneous catalysis (mixed-metal oxides). Studies of small-molecule
models of these systems have revealed numerous instances of effects
of redox inactive metals on electron- and group-transfer reactivity.
However, the heterometallic species directly involved in these transformations
have rarely been structurally characterized and are often generated in situ. We have previously reported the preparation and
structural characterization of multiple series of heterometallic clusters
based on Mn3 and Fe3 cores and described the
effects of Lewis acidity of the heterometal incorporated in these
complexes on cluster reduction potential. To determine the effects
of Lewis acidity of redox inactive metals on group transfer reactivity
in structurally well-defined complexes, we studied [Mn3MO4], [Mn3MO(OH)], and [Fe3MO(OH)]
clusters in oxygen atom transfer (OAT) reactions with phosphine substrates.
The qualitative rate of OAT correlates with the Lewis acidity of the
redox inactive metal, confirming that Lewis acidic metal centers can
affect the chemical reactivity of metal oxo species by modulating
cluster electronics.
%I ACS Publications