Three-membered Rings with Two Heteroatoms including Phosphorus to Bismuth

Etemad‐Moghadam, Guita; Koenig, Max

doi:10.1016/b978-008096518-5.00016-2

Cited by 1 publication

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“…The formation of DPP via a proposed 1,2-diphosphaallyl intermediate 7 especially raises the question as to whether the ring is formed under thermodynamic or kinetic control. Only a few of the possible CR 4 P 2 isomers have been detected so far . Therefore, a comprehensive investigation of the CH 4 P 2 energy hypersurface can provide suggestions for new products and reactive intermediates.…”

Section: Introductionmentioning

confidence: 99%

How the Fourteen Most Stable CH₄P₂ Isomers InterconvertAn ab Initio/NMR Study

et al. 2001

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Energies of minima and TS as well as characteristic NMR chemical shifts are reported for the parent unsaturated phospho-organic molecules with CP2 backbone. Within the 14 relevant isomers of CH4P2, the two most stable structures are 1,2-diphospha-l-propene, 3, and diphosphirane (cyclo-CH2(PH)2, 1, E r el = 8 kJ/mol). The relative energies in kJ/mol at MP2/6-31G(d,p) are 84 for 1,3-diphospha-2-propene, 54 for 1,2-diphospha-2-propene, and for the phosphinidenes, they are 63 (P−PH−CH3) and 102 (P−CH2−PH2). Although the potential intermediate products (PH−CH2−PH, PH−PH−CH2, and cyclo-CH2−PH2−P) of diphosphirane rearrangements have the relative energies 182, 157, and 158 kJ/mol, respectively, and other minima were found to have E r el between 287 and 322 kJ/mol. Rupture of endocyclic bonds of 1a displays a preference for opening the P−C bond toward the CH2−PH−PH structure, which is stabilized by allyl conjugation. The lowest energy pathway for isomerization of 1 has a barrier of 213 kJ/mol and goes via the intermediate cyclo-(CH2)(PH2)(P) toward PH2−PCH2. The calculated energy barriers of CH3−PPH, 3, indicate that this isomer should be kinetically stable as isolated molecule.

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Section: Introductionmentioning

confidence: 99%