Der Zugang zu Phosphor‐reichen Zirconiumkomplexen

The phosphorus analogues of cyclopentadienone, tricyclopentanone,and housene were accessed from bis(cyclopropenyl)diphosphetanedione 3,w hich was prepared by mixing 1,2,3-tris-tert-butylcyclopropenium tetrafluoroborate (1)a nd sodium phosphaethynolate [Na(OCP)(dioxane) n ]. While photolysis of 3 results in decarbonylation, yielding bis(cyclopropenyl)diphosphene 4 and after rearrangement diphosphahousene 5,t hermolysis of 3 leads to phosphatricyclo[2.1.0.0]pentanone 7.M etal-mediated valence isomerization of 7 and subsequent demetalation provides access to phosphacyclopentadienone 12. Scheme 1. Illustrative examples of strained ring systems. Scheme 2. Synthesis of 1,3-diphosphetane-2,4-dione 3.

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Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

Krachko

Ehlers

Nieger

et al. 2018

Angewandte Chemie

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Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

et al. 2018

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The phosphorus analogues of cyclopentadienone, tricyclopentanone, and housene were accessed from bis(cyclopropenyl)diphosphetanedione 3, which was prepared by mixing 1,2,3-tris-tert-butylcyclopropenium tetrafluoroborate (1) and sodium phosphaethynolate [Na(OCP)(dioxane) ]. While photolysis of 3 results in decarbonylation, yielding bis(cyclopropenyl)diphosphene 4 and after rearrangement diphosphahousene 5, thermolysis of 3 leads to phosphatricyclo[2.1.0.0]pentanone 7. Metal-mediated valence isomerization of 7 and subsequent demetalation provides access to phosphacyclopentadienone 12.

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Transient Dipnictyl Analogues of Acrylamides, R−E=E′−CONR₂, and a Related Diphosphadigalletane from Na[OCP] and (R₂N)₂ECl (E, E′=P, As, Ga)

Borger

Corre

Mei

et al. 2019

Chemistry A European J

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The reaction of Na[OCP] with (R2N)2ECl (E=P or As; R=alkyl) granted direct access to transient amine‐substituted diphospha‐ and arsaphospha‐acrylamide analogues, (R2N)E=P(CONR2) 1. Their facile formation allowed for a comprehensive reactivity study. Dimerization yielded the four‐membered rings (R2N)2E2P2(CONR2)2, whereas in the presence of excess Na[OCP], a stepwise [2+2] cycloaddition occured, leading to the sodium salts of carboxotripnictides [(R2N)EP2CO(CONR2)]−. These salts served as a reservoir of 1, either by extrusion of Na[OCP] or by reaction with the appropriate (R2N)2ECl, giving the [4+2]‐cycloaddition products (R2N)EP(C6H10)(CONR2) in the presence of 2,3‐dimethylbutadiene. The formal conjugate addition product K[(tBuO)(R2N)PP(CONR2)] was obtained by reaction of Na[(R2N)PP2CO(CONR2)] with tBuOK. In addition, a rare diphosphadigalletane with a ladder‐type (R2N)2Ga2P2(CONR2)2 core was isolated from the reaction of Na[OCP] with (R2N)2GaCl (R=alkyl). The unprecedented pnictogenyl carboxamide compounds were thoroughly characterized, including single‐crystal X‐ray structure determinations, and mechanisms for their formation were investigated by DFT calculations.

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Der Zugang zu Phosphor‐reichen Zirconiumkomplexen

Cited by 4 publications

References 52 publications

Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

Transient Dipnictyl Analogues of Acrylamides, R−E=E′−CONR₂, and a Related Diphosphadigalletane from Na[OCP] and (R₂N)₂ECl (E, E′=P, As, Ga)

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Der Zugang zu Phosphor‐reichen Zirconiumkomplexen

Cited by 4 publications

References 52 publications

Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene

Transient Dipnictyl Analogues of Acrylamides, R−E=E′−CONR2, and a Related Diphosphadigalletane from Na[OCP] and (R2N)2ECl (E, E′=P, As, Ga)

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Transient Dipnictyl Analogues of Acrylamides, R−E=E′−CONR₂, and a Related Diphosphadigalletane from Na[OCP] and (R₂N)₂ECl (E, E′=P, As, Ga)