/pdf/pseudo-rotation-in-the-hydrolysis-of-phosphate-esters-1uk69x1wju.pdf

The Reaction of Dipotassium Cyclooctatetraenide with Dichlorophenylphosphine. Rearrangements of 9-Phenyl-9-phosphabicyclo[6.1.0]nonatriene and 9-Phenyl-9-phosphabicyclo[4.2.1]nonatriene

Pseudo-rotation in the hydrolysis of phosphate esters

Role of pseudorotation in the stereochemistry of nucleophilic displacement reactions

The Renaissance in Cyclooctatetraene Chemistry

Dibenzo-7-phosphanorbornadiene compounds, RPA (A = C14H10 or anthracene), are investigated as phosphinidene sources upon thermally induced (70-90 °C) anthracene elimination. Analysis of substituent effects reveals that π-donating dialkylamide groups are paramount to successful phosphinidene transfer; poorer π-donors give reduced or no transfer. Substituent steric bulk is also implicated in successful transfer. Molecular beam mass spectrometry (MBMS) studies of each derivative reveal dialkylamide derivatives to be promising precursors for further gas-phase spectroscopic studies of phosphinidenes; in particular, we present evidence of direct detection of the dimethylamide derivative, [Me2N═P]. Kinetic investigations of iPr2NPA thermolysis in 1,3-cyclohexadiene and/or benzene-d6 are consistent with a model of unimolecular fragmentation to yield free phosphinidene [iPr2N═P] as a transient reactive intermediate. This conclusion is probed by density functional theory (DFT) calculations, which favored a mechanistic model featuring free singlet aminophosphinidenes. The breadth of phosphinidene acceptors is expanded to unsaturated substrates beyond 1,3-dienes to include olefins and alkynes; this provides a new synthetic route to valuable amino-substituted phosphiranes and phosphirenes, respectively. Stereoselective phosphinidene transfer to olefins is consistent with singlet phosphinidene reactivity by analogy with the Skell hypothesis for singlet carbene addition to olefins.

/pdf/mechanism-and-scope-of-phosphinidene-transfer-from-dibenzo-7-2y2atyimfm.pdf

The Reaction of Dipotassium Cyclooctatetraenide with Dichlorophenylphosphine. Rearrangements of 9-Phenyl-9-phosphabicyclo[6.1.0]nonatriene and 9-Phenyl-9-phosphabicyclo[4.2.1]nonatriene

Citations

Pseudo-rotation in the hydrolysis of phosphate esters

Role of pseudorotation in the stereochemistry of nucleophilic displacement reactions

The Renaissance in Cyclooctatetraene Chemistry

Mechanism and Scope of Phosphinidene Transfer from Dibenzo-7-phosphanorbornadiene Compounds

The elusive silacyclopropanes; the preparation and properies of a long sought class of organosilicon compounds

Related Papers (5)

Microwave spectra, molecular structure, and dipole moment of phosphirane

Correlation of Rates of Intramolecular Tunneling Processes, with Application to Some Group V Compounds

Pseudo-rotation in the hydrolysis of phosphate esters

The carbene-like behavior of terminal phosphinidene complexes toward olefins. A new access to the phosphirane ring

Stereochemistry of Phosphorus(V) Fluorides