Anionic Transition Metal Hydrides

Darensbourg, Marcetta Y.; Ash, Carlton E.

doi:10.1016/s0065-3055(08)60025-8

Cited by 75 publications

(47 citation statements)

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“…[12,13] Extensive reactivity studies [14] by Darensbourg and co-workers documented the versatile hydridic reactions of anionic tungsten hydrides like [W(CO) 5 (PPh 3 )H] À , and recent measurements by DuBois provided a quantitative measure of the high hydricity. [13] The thermodynamic hydricity of this anionic hydride is 29 kcal mol À1 greater than than that of the cationic cobalt dihydride [CoH 2 (dppe) 2 ]…”

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confidence: 99%

Catalytic Ionic Hydrogenations

Bullock

2004

Chemistry A European J

290

206

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Catalytic ionic hydrogenation of ketones occurs by proton transfer to a ketone from a cationic metal dihydride, followed by hydride transfer from a neutral metal hydride. This contrasts with traditional catalysts for ketone hydrogenation that require binding of the ketone to the metal and subsequent insertion of the ketone into a M-H bond. Ionic hydrogenation catalysts based on the inexpensive metals molybdenum and tungsten have been developed based on mechanistic understanding of the individual steps required in the catalytic reaction.

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confidence: 99%

Catalytic Ionic Hydrogenations

Bullock

2004

Chemistry A European J

290

206

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“…The case of carbonylhydridometallates has been thoroughly studied by Darensbourg et al, whereby evidence for ion-pairing effects was found. [13] As in the case of similar carbonylhydridometallates, e.g. [HFe(CO) 4 ] Ϫ , no ν(MϪH) band is observed.…”

Section: Infrared Spectroscopymentioning

confidence: 86%

“…The monomeric hydride, [HCr(CO) 5 ] Ϫ , reacts readily with traces of H ϩ to yield the binuclear hydride according to Equation (11)Ϫ(13). (11) (12) (13) As in the case of Mo(CO) 6 and W(CO) 6 , the mechanism of the reaction of OH Ϫ with Cr(CO) 6 is thought to involve a transient metallocarboxylic acid species [Equation (14)]. [28] ( 14) Considering the stoichiometry (2 equiv.…”

Section: Preparation Proceduresmentioning

confidence: 99%

“…It must be noted that in the case of Na ϩ [HFe(CO) 4 ] Ϫ evidence has been found for a similar site-selective interaction with an equatorial CO oxygen atom ( Figure 2). [13] …”

Section: Infrared Spectroscopymentioning

confidence: 99%

“…Some properties of these complexes have already been reported by in a more general review dealing with anionic transition metal hydrides. [13] Hexacarbonylchromium, Cr(CO) 6 , was first prepared by Job and Cassal in 1927. [14] It is a stable, nonvolatile colorless solid, and is less toxic and easier to handle than the liquid Fe(CO) 5 .…”

Section: Introductionmentioning

confidence: 99%

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Pentacarbonylhydridochromates M+[HCr(CO)5]−: Reactivity in Organic Synthesis and Homogeneous Catalysis

Brunet

2000

Eur. J. Inorg. Chem.

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Alkali Metals: Inorganic ChemistryBased in part on the article Alkali Metals: Inorganic Chemistry by Francis S. Mair & Ronald Snaith which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Leung

2005

Encyclopedia of Inorganic Chemistry

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This article is updated to cover the literature in the area of inorganic chemistry of alkali metals since 1993. The advancement in instrumentation and spectroscopic techniques in the past decade has provided the researchers with more powerful tools for structure determination of compounds. In this respect, alkalides containing mixed‐sandwich complexes of alkali metal cations, complexes with dimers or chains of alkali metal anions, electrides with alkali metal ions intercalating in zeolite, and interstitial hydride enclosed by an unusual (Li + ) 8 cubic cage have been found or studied by NMR. With the successful preparation of Na 3 N recently, its correct structure has been revealed. The exact composition of ‘NaB 6 ’ has also been determined. The role of alkali metals in trielide clusters of traditional Zintl polyanions has been demonstrated. Trimetallic Li‐Na‐K amides, alkoxide compounds, and highly aggregated cage structures of lithium‐heavier alkali metal alkoxides have been reported.

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Anionic Transition Metal Hydrides

Cited by 75 publications

References 135 publications

Catalytic Ionic Hydrogenations

Catalytic Ionic Hydrogenations

Pentacarbonylhydridochromates M+[HCr(CO)5]−: Reactivity in Organic Synthesis and Homogeneous Catalysis

Alkali Metals: Inorganic ChemistryBased in part on the article Alkali Metals: Inorganic Chemistry by Francis S. Mair & Ronald Snaith which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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