Synthetic, structural, and chemical study of the 1,2-diphosphetene ring

Charrier, Claude; Guilhem, Jean; Mathey, François

doi:10.1021/jo00314a002

Cited by 46 publications

(12 citation statements)

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“…To the best of our knowledge no complex of 1 , 2 , or topologically related unsaturated P-heterocycles has been reported as yet, in which the metal is coordinated to the π-electrons of a vinylic CC double bond in combination with an adjacent P−M σ-bond. As the divergency of the phosphorus lone pairs and the C ring -p z orbitals can be estimated to be in the range between 15° and 35° on the basis of the P−P−C substituent bond angles (Figure ), which range from 101° to 107°, , a simultaneous interaction between both types of donor functions and a suitable transition metal seems to be possible. The divergency of the C ring -p z orbitals of the pronounced convex surface of the π ligand of [(η 6 -2,2-paracyclophane)Cr(CO) 3 ], for example, is just in that range .…”

Section: Introductionmentioning

confidence: 99%

1,2-Diphosphetene, 1,2-Diphosphete, and 1,3-Diphosphete Metal Complexes: Novel Access by Ring Contraction, Cyclodimerization, and Intramolecular Redox Reactions

et al. 1999

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The reaction of [Cr(CO) 5 (THF)] and pentaphenyl-1,2,3-triphospholene affords a single stereoisomer of [(pentaphenyl-1,3-η-1,2,3-triphospholene)(Cr(CO) 5 ) 2 ] (6). Visible light photolysis of 6 causes a ring contraction and [(trans-tetraphenyl-1,2-η-1,2-diphosphetene)(Cr-(CO) 5 ) 2 ] (7a) is formed, whose stereochemistry was elucidated by X-ray crystallography. trans-1,2-Dichloro-3,4-di-tert-butyl-1,2-diphosphetene (2a) and [Fe 2 (CO) 9 ] form the σ complexes 8b), depending on the relative concentration of the starting materials. 8a has been proven to be an intermediate in the formation of 8b. Heating of neat 8b in a vacuum leads to the elimination of the chlorine substituents in an intramolecular redox reaction and [(3,4-di-tert-butyl-η 4 -1,2-diphosphete)-Fe(CO) 3 ] (9a) is formed. This is the first specific reaction, leading to a 1,2-diphosphete complex. 9a and its 1,3-isomer 10a react with [Cr(CO) 5 (THF)] to form the mono-and diaddition products [1-η-{(3,4-di-tert-butyl-η 4 -1,2-diphosphete)Fe(CO) 3 }Cr(CO) 5 ] (9b), [1,2-η-{(3,4-di-tert-butyl-η 4 -1,2-diphosphete)Fe(CO) 3 }(Cr(CO) 5 ) 2 ] (9c), [1-η-{(2,4-di-tert-butyl-η 4 -1,3-diphosphete)Fe(CO) 3 }Cr(CO) 5 ] (10b), and [1,3-η-{(2,4-di-tert-butyl-η 4 -1,3-diphosphete)-Fe(CO) 3 }(Cr(CO) 5 ) 2 ] (10c), respectively. X-ray crystallographic studies for 9c and 10c give some insight into the bonding situation of the compounds. σ-and π-complexing properties of the diphosphete ligands are almost independent of each other and significant back-bonding from the iron atom to the ligand π* orbitals occurs in both cases.

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Section: Introductionmentioning

confidence: 99%

1,2-Diphosphetene, 1,2-Diphosphete, and 1,3-Diphosphete Metal Complexes: Novel Access by Ring Contraction, Cyclodimerization, and Intramolecular Redox Reactions

et al. 1999

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“…The cu-Cfj protons give a characteristic resonance at 5.39 ppm with a *J(H-P) coupling constant of 27 Hz. We suppose that the formation of 2 involves two separate steps, the first one being the formation of the phosphirene complex 3 [Equation (6)]. Indeed, phosphirene complexes are the normal products of the reaction of terminal phosphinidene complexes with alkynes' and we have also shown that it is possible to insert monosubstituted acetylenes into the ring of phosphirene complexes in the presence of a palladium catalyst.'"…”

Section: Resultsmentioning

confidence: 99%

The Reaction of Terminal Phosphinidene Complexes With Electron-Rich Alkynes: A New Approach to the Phosphole Ring

Huy

Mathey

1990

Phosphorus, Sulfur, and Silicon and the Related Elements

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“…Among various (RP) n compounds, pentaphenylcyclopentaphosphine (PhP) 5 ( 1 ) can readily be synthesized by the reaction of dichlorophenylphosphine and magnesium . However, its chemical reactivity has not been significantly examined, except for a few examples: alkylation of 1 with alkyllithium gave mixtures of oligophosphide Li(PhP) n R ( n = 1–4); substitution of 1 with 1,2-dichlorobenzene in the presence of a stoichiometric amount of potassium provided 1,2,3-triphenyl-1,2,3-triphosphaindan; addition of 1 to diphenylacetylene at 240 °C gave a mixture of 1,2-diphenyl-1,2-diphosphetene and pentaphenyltriphospholene; and carbene-phosphinidene adducts formed via the addition of 1 to carbene such as N -heteroacyclic carbenes and bicyclic (alkyl)(amino)carbene . Woollins reagent obtained from 1 and selenium powder are also used in organic synthesis .…”

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confidence: 99%

Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides

et al. 2018

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Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP) with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP) and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.

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Synthetic, structural, and chemical study of the 1,2-diphosphetene ring

Cited by 46 publications

References 3 publications

1,2-Diphosphetene, 1,2-Diphosphete, and 1,3-Diphosphete Metal Complexes: Novel Access by Ring Contraction, Cyclodimerization, and Intramolecular Redox Reactions

1,2-Diphosphetene, 1,2-Diphosphete, and 1,3-Diphosphete Metal Complexes: Novel Access by Ring Contraction, Cyclodimerization, and Intramolecular Redox Reactions

The Reaction of Terminal Phosphinidene Complexes With Electron-Rich Alkynes: A New Approach to the Phosphole Ring

Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides

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