Mechanism of iron pentacarbonyl-catalyzed 1,3-hydrogen shifts

Cowherd, Frank G.; Rosenberg, J. L. Von

doi:10.1021/ja01036a078

Cited by 83 publications

(32 citation statements)

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“…Therefore, no deuterium should be found at position C 2 after isomerization of 1,1-d 2 -allyl system according to mechanism (II). While isomerization of various allyl systems have been proved to occur via mechanism (II) [31,33,35], some typical non-hydride complexes may lead to the formation of -allyl metal hydride as a transient step [31,36]-mechanism (II).…”

Section: Mechanismmentioning

confidence: 99%

Isomerization of alkyl allyl and allyl silyl ethers catalyzed by ruthenium complexes

Krompiec

Kuźnik

Urbala

et al. 2006

Journal of Molecular Catalysis A: Chemical

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Section: Mechanismmentioning

confidence: 99%

Isomerization of alkyl allyl and allyl silyl ethers catalyzed by ruthenium complexes

Krompiec

Kuźnik

Urbala

et al. 2006

Journal of Molecular Catalysis A: Chemical

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“…Both the medium dependence and deuterium uptake observed in the isomerizations 22 -, 23 and 27 + 28 are inconsistent with a direct isopolar sigmatropic [1,6] hydrogen migration (30)(31)(32) or an intramolecular rearrangement of a stable hydridic intermediate. The results d o suggest a mechanism involving a rate determining proton transfer from solvent which may occur with a concerted or synchronous intermolecular loss of a proton from a hydridic intermediate (Scheme 2).…”

Section: Discussionmentioning

confidence: 85%

Acid Catalyzed Rearrangements of Structurally Constrained Tricarbonyl(trans-pentadienyl)iron Cations

Jablonski¹,

Sorensen²

1974

Can. J. Chem.

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. Can. J. Chem. 52, 2085Chem. 52, (1974. Both the tricarbonyl(l,4-dimethylene-ci.~,c.is,tra~ts,cis-hexa-,3-dienyl)iron (secondary) and the tricarbonyl(l,4-dimethylene-5-methyl-cisScis,tra~~s-hexa-1,3-dienyl)iron (tertiary) cations, which cannot convert to a 'lr-cis pentadienyl system via a simple bond rotation, can be prepared at low temperature in strong acid media from their related alcohol complexes. The secondary as well as the tertiary ions rearrange to give the thermodynamically more stable tricarbonyl-(I-alkylcyclohexa-l,3-dienyl)iron cation via an acid catalyzed pseudo first order process. The rate of rearrangement of the secondary ion is much faster than that of the tertiary ion indicating a si~bstantial amount of residual positive charge on the exocyclic (B) carbon in the complexed tratu-pentadienyl carbonii~m ions.C. R. JABLONSKI et T. S. SORENSEN. Can. J. Chem. 52,2085Chem. 52, (1974. Partant descomplexes des alcools correspondants et travaillant a basse temperatureet dans iIn milieu fortement acide, on a pu preparer chacun des cations d~i (dimtthylene-1,4 cis,cis,tratu,ci.s hexadiene-1,3 yl) fer (secondaire) tricarbonyle et du (dimethylene-1,4 methyl-5 cis,cis,trat~s hexadiene-1,3 yl) fer (tertiaire) tricarbonyle q i~i ne peuvent Ctre transformes en iln systeme '11-cis pentadienyle par le moyen d'une simple rotation. L'ion secondaire de mCnie qile le tertiaire se rearrangent pour donner le cation thermodynanliqt~enlent le plus stable (alkyl-l cyclohexadiene-1,) yi) fer tricarbonyle grice Ll n processus depseudo premier ordrecatalyse par les acides. Le rearrangement de I'ion secondaire est beaucoup plus rapide qLle celui de I'ion tertiaire indiqllant qi~'une quantite importante de charge positive residuelle existe sur le carbone (B) exocycliq~~e dans les carbocations complexts trat~s-pentadienyle.[Traduit par le journal]The fact that acyclic tricarbonyl(tm7s-pentaThe obvious structural relationships of the ions dieny1)iron cations (1) are ubiquitous in their 1 and 3 with the profusely studied, yet still conrearrangement to give the related pe17tal7apto-troversial (6) ferrocenyl ion (5) has initiated tricarbonyl(cis-pentadieny1)iron cations (2) has been amply demonstrated (1-3). considerable discussion regarding the electroiiic structure of the trans-pentadienyl ion I. Intimately involved with any discussion of the electronic structure of 1 and 3 is a consideration of the driving force for the rearrangements 1 -+ 2 and 3 + 4.We have previously shown (3) that related trans-cis tricarbonyl(pentadieny1)iron cation pairs (e.g. 1 and 2) rapidly equilibrate a n d that in special circumstances conversion to apental7apro-tricarbonyl(cis-pentadieny1)iron complex is no guarantee of thermodynamic stability. It was of immediate interest then to investigate the stabilization modes available t o tricarbonyl (transCan. J. Chem. Downloaded from www.nrcresearchpress.com by 18.236.120.13 on 05/11/18For personal use only.

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“…Other mechanisms proposed require π-coordination of the alkene to the metal, which then facilitates a 1,3 hydride shift, to yield an enol/enolate or π-oxyallyl intermediate. [1b,3][11c, 14] When the catalyst is a rhodium complex (1 or 3) no significant loss of deuterium content is observed (Table 4). When the catalyst is a ruthenium complex (9, 12 or 14), some loss in deuterium content is observed during the reaction.…”

Section: Resultsmentioning

confidence: 99%

Efficient Isomerization of Allylic Alcohols to Saturated Carbonyl Compounds by Activated Rhodium and Ruthenium Complexes

et al. 2001

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Mechanism of iron pentacarbonyl-catalyzed 1,3-hydrogen shifts

Cited by 83 publications

References 0 publications

Isomerization of alkyl allyl and allyl silyl ethers catalyzed by ruthenium complexes

Isomerization of alkyl allyl and allyl silyl ethers catalyzed by ruthenium complexes

Acid Catalyzed Rearrangements of Structurally Constrained Tricarbonyl(trans-pentadienyl)iron Cations

Efficient Isomerization of Allylic Alcohols to Saturated Carbonyl Compounds by Activated Rhodium and Ruthenium Complexes

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