Ring–chain rearrangements of phosphirane

Nguyen, Minh Tho; Landuyt, Luc; Vanquickenborne, L. G.

doi:10.1039/ft9949001771

Cited by 20 publications

(16 citation statements)

References 24 publications

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“…As a consequence of their high reactivity, these PÀC ring bonds participate in a variety of concerted reactions. An equilibrium occurs at high temperature between phos- [176,177] A related [1,3] halogen shift has been described for 2-halophosphirane complexes [Eq. (67)].…”

Section: Bent Bonds and Strained Ringsmentioning

confidence: 97%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.

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Section: Bent Bonds and Strained Ringsmentioning

confidence: 97%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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“…Gut dokumentiert (und theoretisch untersucht177a) ist die Dissoziation von Phosphiranderivaten in Alkene und niedrig koordinierte Phosphoreinheiten für trivalente Phosphirane,134 Phosphiranoxide,187 Phosphiranium‐Salze188 und Phosphirankomplexe 189. Aus den Ausführungen geht klar hervor, dass Phosphirane hinsichtlich ihrer chemischen Eigenschaften zwischen den Cyclopropanen und den Alken‐Übergangsmetall‐π‐Komplexen einzustufen sind.…”

Section: Besondere Elektronenkonfigurationenunclassified

Phosphaorganische Chemie: Panorama und Perspektiven

Mathey

2003

Angewandte Chemie

198

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Die gesamte phosphororganische Chemie wurde mit Beginn der siebziger Jahre infolge der Entdeckung stabiler phosphororganischer Derivate mit Koordinationszahlen des Phosphors von 1 oder 2 aufgefrischt. Bezüglich ihrer Chemie gleichen diese Verbindungen ihren reinen Kohlenstoff‐Analoga. Dieser Aufsatz widmet sich der Analogie zwischen den Phosphorderivaten und den entsprechenden Alkenen, Alkinen und Carbenen, wobei jede Verbindungsklasse anhand ihrer Synthese, ihrer Reaktivität und ihres Koordinationstyps kurz vorgestellt wird. Des Weiteren werden besondere Elektronenkonfigurationen der Phosphorverbindungen behandelt, darunter P‐P‐Einelektronenbindungen, gespannte Bindungen und aromatische Systeme. Abschließend wird auf mögliche Anwendungen dieser Chemie zur Herstellung molekularer Materialien und in der homogenen Katalyse verwiesen.

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“…We refer the reader again to ref. 5 for the various pathways in other parts of the potential energy surface.…”

Section: Rearrangement Of Phosphiranementioning

confidence: 99%

“…(1), X = H, Cl and Br). In an earlier theoretical study, 5 we demonstrated that the process 1→2 is an energetically concerted process in which the C-P bond breaking (1) † Optimised geometries for the compounds studied are available as supplementary data. For direct electronic access see http://www.rsc.org/ suppdata/p2/b0/b009918j/ ‡ The IUPAC name for ethylphosphinidene is ethylphosphanediyl.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of the ring opening of phosphirane and silirane: contrasting mechanisms of hydrogen migration †

Tran

Nguyen

Veszprémi

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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Ab initio quantum chemical calculations including HF, MP2, CCSD(T), CASSCF(12,12), CASPT2 and B3LYP methods with the basis sets ranging from 6-31G(d,p) to 6-311ϩϩG(3df,2p) were used to establish the contrasting mechanism of the ring-chain rearrangement of both three-membered phosphirane and silirane rings. It is confirmed that the phosphirane ring opening induced by C-P bond cleavage is accompanied by a hydrogen migration from C to P yielding vinylphosphine (H 2 C᎐ ᎐ CHPH 2 ); both motions occur concertedly in a single step with an energy barrier of about 200 ± 15 kJ mol Ϫ1 . In contrast, the preferred ring opening of silirane by C-Si bond cleavage involves a downgrade hydrogen migration from Si to C giving rise to ethylsilylene (H 3 C-CH 2 -SiH) and is associated with a smaller energy barrier of 110 ± 15 kJ mol Ϫ1 (experimental: about 100 kJ mol Ϫ1 for substituted siliranes). There are no significant variations in transition structures geometries obtained either from single determinantal HF-based or multi-configurational CASSCF methods concerning the advance of H-transfer. The solvent effect is also probed using a polarizable continuum model (PCM). Full geometry optimizations within the continuum show that solvation enthalpies are rather small and do not modify the relative ordering of the energy barriers. The contrasting behaviour can be understood by the fact that ethylsilylene is a stable singlet isomer whereas singlet ethylphosphinidene ‡ has a high-energy content and does not exist as an equilibrium structure. Evolution of the Boys localized orbitals suggests that the H-atom migrates as a hydride from C to P and C to Si and as a proton from Si to C. Profiles of static polarizabilities and hardnesses along the IRC pathways are also constructed. In one case, the hardness profile does not follow the "principle of maximum hardness".

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Ring–chain rearrangements of phosphirane

Cited by 20 publications

References 24 publications

Phospha‐Organic Chemistry: Panorama and Perspectives

Phospha‐Organic Chemistry: Panorama and Perspectives

Phosphaorganische Chemie: Panorama und Perspektiven

Theoretical study of the ring opening of phosphirane and silirane: contrasting mechanisms of hydrogen migration †

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