Bicyclic phosphanes. Part 2. Spontaneous dimerization of a constrained bicyclic phosphane. The crystal and molecular structure of a tricyclic compound containing the dioxadiazadiphosphecine ring

Bonningue, Corine; Houalla, D.; Wolf, Robert; Jaud, J.

doi:10.1039/p29830000773

Cited by 22 publications

(21 citation statements)

References 1 publication

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“…The core of the cation can be simply described as a cycloadduct of two molecules of 1. The PÀO and PÀN distances are shorter than those in 1 but similar to the values for related phosphane-PÀO and -PÀN systems [7] and corresponding phosphonium-PÀO [8] and -PÀN systems, [9] respectively. The terminal P1ÀC26 distance of the phosphonium-P atom (175.8(6) pm) is significantly shorter than the other PÀC distances within the cation core and in other phosphonium cations with PÀCH 3 bonds.…”

Section: Dedicated To Professor Gottfried Huttner On the Occasion Of mentioning

confidence: 69%

Formation of a Bowl‐Shaped, Pentacyclic Phosphonium Cage by Methylation of a Nucleophilic Phosphinidene

et al. 2005

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Dedicated to Professor Gottfried Huttner on the occasion of his 68th birthdayPhosphinidenes, that is, carbene-analogous compounds of monovalent phosphorus (phosphanylidenes, RÀP) represent a simple class of valuable electrophilic building blocks in organophosphorus chemistry, which are usually highly reactive transients and therefore difficult to isolate. [1] However, one simple chemical trick that aids the preparation of a room-temperature stable phosphinidene is the intra-or intermolecular addition of a donor group D to the initially electron-deficient phosphorus atom (D!PR); this affords an electron-rich (nucleophilic) phosphinidene, having eight or more valence electrons at the phosphorus center. Several types of donor-stabilized phosphinidenes have already been isolated and used as versatile precursors for the preparation of "free" phosphinidenes such as phospha-Wittig reagents (R 3 P = PR') [2] and related phosphinidene metal complexes (L n M = PR).[3] The intramolecular donor-stabilization of a P(+1) atom is also the reason for the intriguing stability of the nucleophilic phosphinidene 1 (Scheme 1), which has a planar, T-shaped three-coordinate phosphorus atom with 10 valence electrons (10-P-3 system).[4] Although 1 is a promising versatile building block for the synthesis of novel electronically tunable organophosphorus ligands, its reactivity has only been sparingly investigated.[5] The relatively high nucleophilicity at the P atom prompted us to investigate whether alkylation of phosphorus with classical alkylation reagents RX (R = alkyl; X = anionic leaving group) leads to a nucleophilic phosphenium salt A, phosphonium species B, or neutral phosphorane C as possible valence isomers, depending on the electronic nature and steric demand of R and X, respectively (Scheme 1).Here we report the surprising formation of the unusual phosphonium cage cation in 2, which results from a domino cyclization of two molecules of 1 in the presence of methyl trifluoromethylsulfonate (MeOTf). When a solution of MeOTf in CH 2 Cl 2 was added to a solution of 1 in CH 2 Cl 2 in the molar ratio of 1:1 at 20 8C, a rapid reaction occurs ( 31 P NMR monitoring), affording the unexpected phosphonium salt 2 [Eq. (1)]. The latter is insoluble in hydrocarbon solvents and other nonpolar solvents and can be isolated in the form of a colorless solid in 35 % yield. The yield can be increased up to 78 % by changing the molar ratio of the starting materials MeOTf and 1 to 1:2. Interestingly, compound 2 results also exclusively even if a solution of 1 in CH 2 Cl 2 is slowly added to a very large molar excess or even by using neat MeOTf at room temperature or below (À10 8C). The composition and constitution of 2 was established by EI-FAB and ESI (electrospray ionization) mass spectrometry Scheme 1. The possible valence isomers A, B, and C formed by alkylation of 1 with RX (R = alkyl, X = anionic leaving group; ET = electron transfer.

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Section: Dedicated To Professor Gottfried Huttner On the Occasion Of mentioning

confidence: 69%

Formation of a Bowl‐Shaped, Pentacyclic Phosphonium Cage by Methylation of a Nucleophilic Phosphinidene

et al. 2005

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“…This dimerization of the ADPO fragment is surprising because it is not characteristic of ADPO chemistry. Saturated analogs of ADPO have been observed to dimerize in this fashion [29,30] without the need for a metal catalyst (Scheme 2), but ADPO has resisted undergoing the analogous reaction.…”

Section: Adpo-fe( Co)-tsmentioning

confidence: 99%

“…The ADPO dimer unit has a syn configuration in (ADP0)2Fe(CO)3 in which both phosphorus lone pairs of electrons (coordinated to iron) are on the same side of the central 10-membered ring. Dimers of the saturated analogs of ADPO have an anti configuration for the phosphorus lone pairs of electrons [29]. The dimers of [3.3.0]bicyclic ring systems containing 8-Ge-4 centers also possess an anti configuration about the central 10-membered ring [39].…”

Section: Adpo-fe( Co)-tsmentioning

confidence: 99%

The syntheses and structures of iron carbonyl adducts of tricoordinated hypervalent phosphorus compounds

Arduengo

Lattman

Dixon

et al. 1991

Heteroatom Chemistry

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“…The design of molecular structures with phosphate and phosphonate functions in their skeletons has been achieved [4][5][6]. The oligomerizations of alkylene phosphites and amidophosphites have been carried out [7][8][9]. In these cases, mixtures of oligoalkylene cyclophosphites (amidophosphites) were formed.…”

Section: Introductionmentioning

confidence: 99%

New types of phosphorus-containing crown ethers

Nifantyev¹,

Rasadkina²,

Yankovich³

et al. 1998

Heteroatom Chem.

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Bicyclic phosphanes. Part 2. Spontaneous dimerization of a constrained bicyclic phosphane. The crystal and molecular structure of a tricyclic compound containing the dioxadiazadiphosphecine ring

Abstract: Das durch 1:1‐molare Umsetzung des Diols (I) mit dem Phosphin (II) gebildete bicyclische Phosphin (III) dimerisiert spontan unter Spaltung und Neubildung zweier P‐O‐Bindungen zu dem einzigen Produkt (IV).

Cited by 22 publications

References 1 publication

Formation of a Bowl‐Shaped, Pentacyclic Phosphonium Cage by Methylation of a Nucleophilic Phosphinidene

Formation of a Bowl‐Shaped, Pentacyclic Phosphonium Cage by Methylation of a Nucleophilic Phosphinidene

The syntheses and structures of iron carbonyl adducts of tricoordinated hypervalent phosphorus compounds

New types of phosphorus-containing crown ethers

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