Mechanismus der Cyclocotrimerisierung von Diethyl(hydrido)thiophosphor mit Alkinen

Lindner, Ekkehard; Krieg, Claus‐Peter; Hiller, W.; Fawzi, Riad

doi:10.1002/ange.19840960719

Cited by 22 publications

(3 citation statements)

References 13 publications

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“…The C a alkene carbon atoms, sbonded to iron, resonate at 193.3 ppm. This is a normal ppm value for an Fe-C(sp 2 ) [9,11,[72][73][74] carbon atom and comparable with that of 198.0 ppm in 10a. The C b alkene carbon atom is observed at 128.0 ppm, which is within the range generally observed for sp 2 -alkene carbon atoms.…”

Section: Complex 12d and Compound 13supporting

confidence: 75%

1,3-Dipolar cycloaddition to the FeSC fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate

Siebenlist

Frühauf

Kooijman

et al. 2002

Inorganica Chimica Acta

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Section: Complex 12d and Compound 13supporting

confidence: 75%

1,3-Dipolar cycloaddition to the FeSC fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate

Siebenlist

Frühauf

Kooijman

et al. 2002

Inorganica Chimica Acta

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“…The Fe(2)−C(3) bond distance of 1.965(6) Å is within the range generally observed for Fe−C(sp 2 ) bonds. − The Fe−C bond distances in the allyl part are almost identical with those observed for Fe 2 (CO) 6 [HCC(C(O)CH 3 )C(O)CH 3 )S- t -Bu] 44 and are on average 0.10 Å shorter than in Ru 2 (CO) 6 [CH 3 CC(H)C(H)NC(CH 3 ) 2 ], which is expected due to the smaller covalent radius of Fe. The new amine fragment is σ(N)-coordinated to Fe(2) at a distance of 2.064(5) Å, comparable to the Fe−N bond distance of 2.030(8) Å found in the isostructural complex Fe 2 (CO) 5 [ i -PrNCHCHN( i -Pr)C(O)C(Me)CNEt 2 ] .…”

Section: Resultssupporting

confidence: 71%

1,3-Dipolar Cycloaddition to the Fe−XC Fragment 18. Chemoselectivity in the Addition of Activated Alkynes across the Fe−OC Fragment vs the Fe−NC Fragment in Chelate (α-Imino ester)tricarbonyliron Complexes

Siebenlist¹,

Beurs²,

Feiken³

et al. 2000

Organometallics

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In situ prepared chelate complexes Fe(CO) 3 (R 1 NdC(R 2 )C(R 3 )dO) (R 1 ) alkyl, R 2 ) H, R 3 ) O-alkyl) (7a-j) react with dimethyl acetylenedicarboxylate (DMAD) via a 1,3-dipolar cycloaddition reaction to form four products as a result of cycloaddition to both the Fe-Od C and the Fe-NdC fragments. The main product is the Fe(CO) 3 (butenolide) complex (10), which results from cycloaddition to the Fe-OdC fragment, indicating that this fragment is more reactive than the Fe-NdC fragment. Complexes 10, 11, 13, and 15 have been characterized by spectroscopy (IR, 1 H and 13 C NMR, FD-mass) and by elemental analyses. The molecular structures of all four types of complexes (10d, 11a, 13c, and 15h) have been established by single-crystal X-ray diffraction. The product formation and distribution is determined by both the R 1 and the R 3 substituents. Reaction with the less activated alkyne methyl propynoate (MP) results, in a slow reaction, exclusively in cycloaddition to the Fe-OdC fragment with formation of two products depending on the additional ligand offered. Uptake of an additional CO ligand leads to the Fe(CO) 3 (butenolide) complex 16, which is formed exclusively as one of the possible regioisomers with the former ketone carbon atom C-C connected to the ester-substituted alkyne carbon atom. When MP also acts as an additional ligand, the tricyclic complexes 20 are formed, which consist of three five-membered rings. Complexes 20 are also obtained in almost quantitative yield by irradiation of 16 in the presence of MP. Similarly, complexes 19 are obtained by irradiation of 10 in the presence of MP. The molecular structure has been confirmed by an X-ray structure determination of 19c. When complexes 10 are refluxed in THF and subsequently reacted with water at room temperature, the organic butenolide derivatives 21 with an exocyclic enamine function are obtained. The molecular structure has been established by an X-ray structure determination of 21c. Reaction of 10 under 50 bar of CO pressure at 115 °C results in the liberation of the intact butenolide heterocycles (22) together with some side products. Scheme 1. Reactions of Fe(CO) 2 L(R-DAB), Fe(CO) 3 (r-imino ketone), and Ru(CO) 3 (R-DAB) with the Electron-Deficient Alkynes DMAD and MP

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“…(2) angegebene Reaktionsablauf erkllrt auch die Notwendigkeit des PPh,-Zusatzes bei der Synthese von 3a -d. Der Phosphanligand verschiebt das Gleichgewicht 3a%4a zugunsten von 3a und erschwert damit die Weiterreaktion zu 7a. Diese ist grundsatzlich.…”

Section: Metal-containing Heterocycles Preparationunclassified

Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXI Das Verhalten von η²‐Thiophosphinito‐Komplexen des Cobalts gegenüber elektronenarmen Alkinen

Lindner¹,

Frick²,

Stängle³

et al. 1989

Chem. Ber.

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In Gegenwart von PPh3 setzt sich der (q2-Thiophosphinito)co-Nach einer Rbntgenstrukturanalyse kristallisiert 3 b in der Raumgruppe Pi rnit 2 = 2. In dem planaren Fiinfring besitzt Cobalt eine trigonalbipyramidale Geometrie. Aus 3 a und 2a erhilt man iiber das nicht isolierbare Cyclotrimerisat 6a durch dessen hydrolytischen Abbau und Umlagerung das Furanderivat 7% welches bei Abwesenheit von PPh3 auch direkt durch Reaktion von 1 rnit iiberschiissigem 2s entsteht. Die Umsetzung von 3 b rnit dem gemischt substituierten Alkin CH3C = CC02CH3 (2e) liefert die isomeren Furanderivate 8 und 9.

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Mechanismus der Cyclocotrimerisierung von Diethyl(hydrido)thiophosphor mit Alkinen

Cited by 22 publications

References 13 publications

1,3-Dipolar cycloaddition to the FeSC fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate

1,3-Dipolar cycloaddition to the FeSC fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate

1,3-Dipolar Cycloaddition to the Fe−XC Fragment 18. Chemoselectivity in the Addition of Activated Alkynes across the Fe−OC Fragment vs the Fe−NC Fragment in Chelate (α-Imino ester)tricarbonyliron Complexes

Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXI Das Verhalten von η²‐Thiophosphinito‐Komplexen des Cobalts gegenüber elektronenarmen Alkinen

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Mechanismus der Cyclocotrimerisierung von Diethyl(hydrido)thiophosphor mit Alkinen

Cited by 22 publications

References 13 publications

1,3-Dipolar cycloaddition to the FeSC fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate

1,3-Dipolar cycloaddition to the FeSC fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate

1,3-Dipolar Cycloaddition to the Fe−XC Fragment 18. Chemoselectivity in the Addition of Activated Alkynes across the Fe−OC Fragment vs the Fe−NC Fragment in Chelate (α-Imino ester)tricarbonyliron Complexes

Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXI Das Verhalten von η2‐Thiophosphinito‐Komplexen des Cobalts gegenüber elektronenarmen Alkinen

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Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXI Das Verhalten von η²‐Thiophosphinito‐Komplexen des Cobalts gegenüber elektronenarmen Alkinen