The {development|improvement} of homogeneous catalysis is enabled by the availability of a {rich|wealthy} toolkit of kinetics experiments, {such as|like|including|for example|for instance|which include} the Hg-drop test, that differentiate catalytic activity at ligand-supported metal complexes from {potential|possible|prospective} heterogeneous catalysts derived from decomposition of molecular species. Metal-organic frameworks (MOFs) have garnered {significant|substantial|considerable|important} {attention|interest|focus|consideration} as platforms for catalysis at site-isolated, interstitial catalyst sights. {Unlike|In contrast to|As opposed to} homogeneous catalysis, {relatively|fairly|comparatively|reasonably|somewhat} {few|couple of|handful of} {strategies|methods|techniques|approaches|tactics} {have been|happen to be|have already been} {advanced|sophisticated} to evaluate the origin of catalytic activity in MOF-promoted reactions. {Many|Numerous|Several|A lot of|Quite a few|Lots of} {of the|from the|in the|on the|with the|of your} MOFs {that have|which have} been examined as {potential|possible|prospective} catalysts are comprised of molecular constituents that represent viable catalysts {in the|within the|inside the} absence {of the|from the|in the|on the|with the|of your} extended MOF lattice, and {thus|therefore|hence|as a result} interfacial {sites|websites|web sites|internet sites|web-sites|web pages} and leached homogeneous species represent {potential|possible|prospective} sources of catalyst activity. {Here|Right here}, we demonstrate that {analysis|evaluation} of deuterium kinetic isotope effects (KIEs) and olefin epoxidation diastereoselectivity {provides|offers|gives|supplies|delivers} direct probes {of the|from the|in the|on the|with the|of your} origin of catalytic activity in MOF-promoted oxidation reactions. These analyses {support|assistance|help} direct involvement of lattice-based Fe {sites|websites|web sites|internet sites|web-sites|web pages} {in the|within the|inside the} turnover-limiting step of C–H activation with Fe-MOF-74-based {materials|supplies|components} (i.e., the MOF functions as a bona fide catalyst) and {evidence|proof} that Cu2-based MOF MIL-125-Cu2O2 functions as a solid-state initiator for solution-phase oxidation chemistry and {is not|isn’t|just isn’t|is just not|will not be} involved {in the|within the|inside the} turnover limiting step (i.e., the MOF {does not|doesn’t|will not} function as a catalyst). We anticipate that the {simple|easy|straightforward|basic|uncomplicated|very simple} experiments described {here|right here} will {provide|offer|supply|give|present|deliver} a {valuable|beneficial|useful|worthwhile|precious|important} tool for clarifying the {role|function|part} of MOFs in C–H oxidation reactions. Methyl (S)-3-bromo-2-methylpropanoate site (Diacetoxyiodo)benzene structure PMID:24455443
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