X-Ray Determination of the Structure of Anhydrous Diphenylcyclopropenone. Variations of the Molecular Geometry Due to Hydrogen Bonding

Tsukada, Harumichi; Shimanouchi, Hirotaka; Sasada, Yoshio

doi:10.1246/cl.1974.639

Cited by 21 publications

(16 citation statements)

References 6 publications

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“…The differences between the lengths of the formally single CϪC bonds and the double CϭC bond are 0.051 and 0.054 Å , which are similar to the analogous length differences in 2,3-diphenylcyclopropenone. [19] The CϭO, FeϪC, and carbonϪcarbon bonds of the cyclopentadienyl rings, as well as the geometrical parameters of the ferrocene sandwiches, are close to standard values. [20]  Two separate oxidations are observed, the second of which is affected by adsorption phenomena at the electrode surface.…”

Section: Resultsmentioning

confidence: 62%

2,3‐Diferrocenylcyclopropenone: Synthesis, Structure, and Some Chemical and Electrochemical Properties

et al. 2003

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Alkylation of ferrocene with tetrachlorocyclopropene in the presence of AlCl 3 followed by aqueous workup affords 2,3-diferrocenylcyclopropenone in high yield. We have studied some of this ketone's chemical transformations and electrochemical properties. 2,3-Diferrocenylcyclopropenone withstands thermolysis; it is stable in an acidic medium; the action of tetrafluoroboric acid−diethyl ether results in the formation of diferrocenyl(hydroxy)cyclopropenylium tetrafluoroborate; nucleophiles, including methyllithium and lithium aluminum

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Section: Resultsmentioning

confidence: 62%

2,3‐Diferrocenylcyclopropenone: Synthesis, Structure, and Some Chemical and Electrochemical Properties

et al. 2003

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“…Bond lengths in the cyclopropenyl ring with C−C distances close to the average value of 139 pm confirm a delocalized π‐bond with an approach to an aromatic cyclopropenyl ring for 14 . Delocalization is more pronounced than in uncoordinated diphenylcyclopropenone and supported by the coordination of the O atom to the Lewis acid. In contrast, 15 shows a localized bonding situation in the C 3 ring with C−C distances of 150 (2x) and 131 pm.…”

Section: Resultsmentioning

confidence: 95%

“…The GaÀO distance (207.8(1) pm)c orresponds to the standard value of dative O!Ga bonds, and the C=Ob ond lengths is with 123.8 (2) pm similar to that of the startingc yclopropenone. [18] The sum of the GaC 2 angles (3558)v erifies an almost ideal planar coordination of the Ga atom by the Ca toms with the GaÀOb ond perpendicular to the plane.S imilar to the Al com-pound 14 an essentially electrostatic interaction between Ga and Om ay be derived.T he 31 PNMR resonance was found at d = À7.7 ppm and corresponds to the value assigned to 14 in the solid state (see above).…”

Section: Reactionswith Cyclopropenone and Related Compoundsmentioning

confidence: 99%

Al/P‐ and Ga/P‐Based Frustrated Lewis Pairs and Electronically Unsaturated Substrates: Ring Cleavage and Ring Closure, C−C and C−N Bond Formation

Pleschka

Uebing

Lange

et al. 2019

Chemistry A European J

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Al/P‐ and Ga/P‐based frustrated Lewis pairs (FLPs) reacted with an azirine under mild conditions under cleavage of the heterocycle on two different positions. Opening of the C−C bond yielded an unusual nitrile–ylide adduct in which a C−N moiety coordinated to the FLP backbone. Cleavage of a C−N bond afforded the thermodynamically favored enamine adduct with the N atom bound to P and Al or Ga atoms. Ring closure was observed upon treatment of an Al/P FLP with electronically unsaturated substrates (4‐(1‐cyclohexenyl)‐1‐aza‐but‐1‐en‐3‐ynes) and yielded by C−N bond formation hexahydroquinoline derivatives, which coordinated to the FLP through P−C and Al−C bonds. Diphenylcyclopropenone showed a diverse reactivity, which depending on steric shielding and the polarizing effect of Al or Ga atoms afforded different products. An AltBu2/P FLP yielded an adduct with the C=O group coordinated to P and Al. The dineopentyl derivative gave an equilibrium mixture consisting of a similar product and a simple adduct with O bound to Al and a three‐coordinate P atom. Both compounds co‐crystallize. The Ga/P FLP only formed the simple adduct with the same substrate. Rearrangement resulted in all cases in C3‐ring cleavage and migration of a mesityl group from P to a former ring C atom by C−C bond formation. Diphenylthiocyclopropenone (evidence for the presence of P=C bonds) and an imine derivative afforded similar products.

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“…Such weak interactions are important for the reversibility of adduct formation . The C=C distance in the cyclopropene ring (131.0(2) pm) resembles that of the starting cyclopropenone compound . A singlet is observed in the 31 P{ 1 H} NMR spectrum at δ =21.7 ppm, which shifts towards higher field relative to the resonances of compounds 2 and 3 and closer to the resonance of the uncoordinated FLP 1 .…”

Section: Resultsmentioning

confidence: 98%

Reactions of an Aluminium/Phosphorus Frustrated Lewis Pair (FLP) with α,β‐Unsaturated Carbonyl Compounds: FLPs as Efficient Two‐Electron Reductants with the Formation of Enolates, a cis‐Enediolate, and an Allene

Lange

Tendyck

Wegener

et al. 2018

Chemistry A European J

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The Al/P-based frustrated Lewis pair (FLP) Mes P-C(AltBu) =C(H)Ph (1; Mes=mesityl) reacted as an efficient two-electron reductant with benzil to afford a cis-enediolate that was coordinated to the FLP through P-O and Al-O bonds and the formation of a seven-membered heterocycle (2). The phosphorus atom is oxidised from +III to +V. Similar heterocycles (3 a to 3 f) were formed if 1 was treated with various enones (acrolein, acrylate, acrylamide). The resulting enolates are bound to the FLP through P-C and Al-O bonds. Cyclopropenone gave an adduct (4) with the C=O bond coordinated by P and Al. Ynones gave a fascinating variety of different structures. 1,3-Diphenylprop-2-yn-1-one afforded a remarkable allene-type moiety with two cumulated C=C bonds (5); 3-hexyn-2-one yielded a ligand with two conjugated C=C bonds by C-H bond activation at the carbonyl methyl group (7); and 4-(trimethylsilyl)-3-butyn-2-one reacted by C-H bond cleavage, formation of an enolate group with a terminal C=C bond, and shift of the proton to the P atom (8). The C≡C bond was not affected. Allene compound 5 rearranged at elevated temperature and in daylight through the formation of a tricyclic compound by C-H bond activation and C-C bond formation. DFT calculations on this unusual rearrangement suggest insertion of the central allene C atom into the C-H bond of a methyl group and the intermediate formation of a C ring.

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X-Ray Determination of the Structure of Anhydrous Diphenylcyclopropenone. Variations of the Molecular Geometry Due to Hydrogen Bonding

Cited by 21 publications

References 6 publications

2,3‐Diferrocenylcyclopropenone: Synthesis, Structure, and Some Chemical and Electrochemical Properties

2,3‐Diferrocenylcyclopropenone: Synthesis, Structure, and Some Chemical and Electrochemical Properties

Al/P‐ and Ga/P‐Based Frustrated Lewis Pairs and Electronically Unsaturated Substrates: Ring Cleavage and Ring Closure, C−C and C−N Bond Formation

Reactions of an Aluminium/Phosphorus Frustrated Lewis Pair (FLP) with α,β‐Unsaturated Carbonyl Compounds: FLPs as Efficient Two‐Electron Reductants with the Formation of Enolates, a cis‐Enediolate, and an Allene

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