2018
DOI: 10.1002/zaac.201800045
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Abstract: It is well known that a metal‐bound hydroxido ligand is an efficient nucleophile around neutral pH. In a mechanistic sense, the presence and chemical reactivity of the coordinated hydroxido nucleophile are frequently invoked both in biomimetic chemistry and in numerous examples of hydrolytic metalloenzymes. In this review, we explore the background of this chemistry in order to attempt to trace the thinking which led to what is now a fully accepted mechanistic pathway.

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Cited by 8 publications
(4 citation statements)
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References 267 publications
(320 reference statements)
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“…The lack of oxygen atoms in 1 and NH 3 clearly shows that the source of oxygen impurities is not precursor-related. The sources could include residual oxygen and moisture in the ALD reaction chamber, etching of the inductively coupled plasma quartz tube, or post-deposition oxidation of GaN films (GaN, Δ f G ° = −78 kJ/mol –1 ; Ga 2 O 3 , Δ f G ° = −998 kJ/mol –1 ) . The higher tolerance of 1 to oxygen and moisture over GaMe 3 and Ga­(NMe 2 ) 3 gives great promise to completely removing the oxygen impurities.…”
Section: Resultsmentioning
confidence: 99%
“…The pH optima vary from 7.8 to 11, with one example having a maximum at pH 6. Common to all of these systems is that the active species is a metal‐bound hydroxido (M−OH) nucleophile, [102] analogous to the majority of known homogeneous counterparts [28, 32, 44–50, 103, 104] …”
Section: Catalytic Activitymentioning
confidence: 99%
“…The pH optima vary from 7.8 to 11,w ith one example having amaximum at pH 6. Common to all of these systems is that the actives peciesi sametal-bound hydroxido (MÀOH) nucleophile, [102] analogous to the majority of known homogeneous counterparts. [28, 32, 44-50, 103, 104] The substrates employed are typically "activated" phosphate esters:c ommon examples include 2,4-DNPP,2 ,4-BDNPP,4 -BNPP,4 -NPP,a nd HPNPP and those less commonly employed are ENPMP,E 3,5DCPMPT, and H3,5DCPMPT ( Tables 1a nd 2).…”
Section: Catalytic Activitymentioning
confidence: 99%
“…Species containing such reactive M−OH, M−OR or M−NR 2 linkages are key intermediates in various catalytic processes, ranging from commodity industrial processes (like the Wacker reaction) [6] to biocatalysis, e. g. in metalloenzymes like carbonic anhydrase or alcohol deshydrogenase [7] . Furthermore, the nucleophilicity of covalent metal hydroxides played an important role in the historic development Coordination Chemistry [8] . In contrast with the usually well‐defined nature of M−C bonds, the chemistry of M−OH or M−OR ensembles is often complicated by their tendency to cancel its basicity forming multinuclear aggregates, to experience irreversible hydrogen elimination processes, or simply by their facile hydrolysis with the slightest moisture traces.…”
Section: Introductionmentioning
confidence: 99%