Hydridübertragung durch Hydridokomplexe, ionische Hydrierung von Aldehyden und Ketonen sowie Struktur eines Alkoholkomplexes

Song, Jeong-Sup; Szalda, David J.; Bullock, R. Morris; Lawrie, Christophe J. C.; Rodkin, Mikhail A.; Norton, Jack R.

doi:10.1002/ange.19921040944

Cited by 16 publications

(18 citation statements)

References 20 publications

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“…Stoichiometric ionic hydrogenations of ketones can be accomplished under mild conditions by addition of a strong acid (HOTf; OTf = OSO 2 CF 3 ) to solutions containing ketones and metal hydrides. [18] These reactions document that transition metal hydrides can function as hydride donors in the presence of a strong acid. As shown in generalized form in Eq.…”

Section: -H )]mentioning

confidence: 99%

Catalytic Deoxygenation of 1,2‐Propanediol to Give n‐Propanol

et al. 2009

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Deoxygenation of 1,2-propanediol (1.0 M in sulfolane) catalyzed by bis(dicarbonyl)(m-hydrido)(pentamethylcyclopentadiene)ruthenium trifluo-+ OTf À ) (0.5 mol%) at 110 8C under hydrogen (750 psi) in the presence of trifluoromethanesulfonic acid (HOTf) (60 mM) gives n-propanol as the major product, indicating high selectivity for deoxygenation of the internal hydroxy group over the terminal hydroxy group of the diol. The deoxygenation of 1,2-propanediol is strongly influenced by the concentration of acid, giving faster rates and proceeding to higher conversions as the concentration of HOTf is increased. Propionaldehyde was observed as an intermediate, beingformed through acid-catalyzed dehydration of 1,2-propanediol. This aldehyde is hydrogenated to npropanol through an ionic pathway involving protonation of the aldehyde, followed by hydride transfer from the neutral hydride, dicarbonyl(pentamethylcyclopentadiene)ruthenium hydride [Cp*Ru(CO) 2 H]. The proposed mechanism for the deoxygenation/hydrogenation reaction involves formation of a highly acidic dihydrogen complex [Cp*Ru(CO) 2

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Section: -H )]mentioning

confidence: 99%

Catalytic Deoxygenation of 1,2‐Propanediol to Give n‐Propanol

et al. 2009

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“…Recently, there has been a considerable interest in understanding the mechanisms of hydride transfer reactions for the C 5 H 5 M(CO) 3 H ͑where MϭCr, W, Mo͒ type of complexes. 1 Several derivatives of the C 5 H 5 M(CO) 3 H complexes have been studied and explored as catalysts for protonation of olefins, aldehydes, and ketones.…”

Section: Introductionmentioning

confidence: 99%

“…1 Several derivatives of the C 5 H 5 M(CO) 3 H complexes have been studied and explored as catalysts for protonation of olefins, aldehydes, and ketones. Bullock and Song have demonstrated that the rate of hydride transfer for some derivatives of C 5 H 5 M(CO) 3 H is highly dependent on steric factors, temperature, and the strength of the M-H bond. [2][3][4] The C 5 H 5 M(CO) 3 H complex can function as a hydride, proton, or hydrogen donor and its conjugate is quite reactive and can react with a wide variety of ligands.…”

Section: Introductionmentioning

confidence: 99%

“…Bullock and Song have demonstrated that the rate of hydride transfer for some derivatives of C 5 H 5 M(CO) 3 H is highly dependent on steric factors, temperature, and the strength of the M-H bond. [2][3][4] The C 5 H 5 M(CO) 3 H complex can function as a hydride, proton, or hydrogen donor and its conjugate is quite reactive and can react with a wide variety of ligands. For example, the conjugated form of C 5 H 5 W͑CO) 3 H has been demonstrated to bind onto MgO and Al 2 O 3 surfaces via the carbonyl ligands.…”

Section: Introductionmentioning

confidence: 99%

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Microwave spectra and the metal-hydrogen bond lengths for the C5H5Mo(CO)3H and C5H5W(CO)3H complexes

Tanjaroon

Keck

Sebonia

et al. 2004

The Journal of Chemical Physics

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The measurements of rotational spectra and metal-hydrogen bond lengths for molybdenum and tungsten hydride complexes were recently completed in our laboratory. The W-H and Mo-H bond lengths were obtained from high resolution rotational spectra of C5H5Mo(CO)3H, C5H5W(CO)3H, C5H5Mo(CO)3D, and C5H5W(CO)3D. Data for five molybdenum and four tungsten isotopomers were obtained for both the normal and deuterium-substituted species. The asymmetric-top rotational parameters A, B, C, DeltaJ, and deltaJ were determined from the least-squares fits and these results indicate that the structures of these complexes are nearly rigid. The hydrogen bond lengths were determined for both complexes using Kraitchman analyses. The molybdenum-hydrogen bond length for the C5H5Mo(CO)3H complex is rMo-H=1.80(1) A. The tungsten-hydrogen bond length for the C5H5W(CO)3H complex is rW-H=1.79(4) A. Density functional theory (DFT) calculations of the structures were performed to obtain the optimized theoretical structures for C5H5Mo(CO)3H and C5H5W(CO)3H. Results obtained from the DFT calculations are in good agreement with the experimental parameters, and the Mo-H value is in good agreement with previously reported Mo-H bond lengths for similar complexes.

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“…Distances r(HÁÁÁH) in [Å] can be obtained from Eq. (11) [12,27,[91][92][93][94][95] where m is the NMR frequency in MHz and DR 1 (min) = 1/T 1 (min)(add) -1/T 1 (min)(WH). rðH Á Á Á HÞ ¼ 5:817ðm Á DR1ðminÞÞ À1=6 ð11Þ…”

Section: Preparation Of Mer-w(co)(no)[ochme 2 ](Pme 3 ) 3 (7)mentioning

confidence: 99%