1998
DOI: 10.1021/ja980672d
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A Useful Method for Preparing Iridium Alkoxides and a Study of Their Catalytic Decomposition by Iridium Cations:  A New Mode of β-Hydride Elimination for Coordinatively Saturated Metal Alkoxides

Abstract: Compared with late transition metal alkyls, the corresponding metal alkoxides are difficult to prepare, especially if C-H bonds at the carbon connected to the oxygen atom are present. 1b Attempts to obtain these compounds by the displacement of halides or other good leaving groups from transition metal centers with alkali metal alkoxides (in analogy to the general method used to prepare metal alkyls) often lead to the corresponding metal hydrides. In fact, this occurs so frequently that the treatment of meta… Show more

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Cited by 68 publications
(39 citation statements)
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“…Additional experiments would be needed to elucidate the mechanistic reasons for acceleration provided by the NH phosphine, which is somewhat modest. However, under the basic conditions employed, one can imagine that the NH may be deprotonated and the resulting pendant base may assist in one or more steps of the transfer hydrogenation, for example by deprotonating the alcohol as it binds to the metal and forms an alkoxide, several examples of which are known on Cp*Ir fragments [64][65][66].…”
Section: Model Studies On Other Metal Fragmentsmentioning
confidence: 99%
“…Additional experiments would be needed to elucidate the mechanistic reasons for acceleration provided by the NH phosphine, which is somewhat modest. However, under the basic conditions employed, one can imagine that the NH may be deprotonated and the resulting pendant base may assist in one or more steps of the transfer hydrogenation, for example by deprotonating the alcohol as it binds to the metal and forms an alkoxide, several examples of which are known on Cp*Ir fragments [64][65][66].…”
Section: Model Studies On Other Metal Fragmentsmentioning
confidence: 99%
“…18 The picture presented in the inner sphere mechanism (4) formally requires an expansion of the coordinatively and electronically saturated metal and it has been suggested that prior ligand dissociation must occur 24 although some pathways are thought to involve the cooperative participation of two metal centres. 25 A recent study of a Cp*Ir complex provided evidence for displacement of the Cp* ligand which may be relevant to hydrogen transfer catalysis by providing the assumed required vacant coordination site. 26 The transfer hydrogenation of imines to amines and the corresponding reverse reaction are expected to show significant differences to the ketone/alcohol reaction because of the differences in basicity, susceptibility to nucleophilic attack and their ability to bind to metal ions.…”
Section: Introductionmentioning
confidence: 99%
“…Complex 2 is coordinatively saturated and therefore a traditional b-H elimination is unlikely unless one of the phosphine arms dissociates. Mechanisms for b-H elimination www.chemeurj.org from metal alkoxides, which do not require a vacant coordination site were proposed, [10] and recently a mechanism has been proposed for the hydrogenation of CO 2 by the iPr analogue of 1. [11] Herein, we would like to suggest a new mechanistic variant that is strictly intramolecular (see Figure 1 for the corresponding potential-energy surface).…”
mentioning
confidence: 99%