6829-52-3Relevant articles and documents
Reinvestigation of the HCP electronic spectrum: Experimental determination of D0 for the X state and observation of hyperfine quantum beats in the B state
Mason, Martin A.,Lehmann, Kevin K.
, p. 5184 - 5190 (1993)
In the laser-induced fluorescence spectrum of HCP, a sharp decrease in fluorescence intensity was observed at 41 680 cm-1.This diminuation in emission intensity is due to a rotationally mediated coupling of the excited vibronic level with the dissociative continuum of the X state; this has allowed us to place an upper limit on D0 for the ground electronic state.A lower limit for D0 can be placed at 41 650 cm-1 since strong emission was observed below this excitation energy.Using the assignments of Johns et al. as a guide, fluorescence decays were recorded from the two B state vibronic bands to determine lifetimes.In addition to determining an unusually long lifetime for both states, the decays were seen to be modulated at four frequencies resulting from the coherent excitation of four nuclear hyperfine levels.This increase in lifetime and magnetic hyperfine interaction arises from a mixing of three singlet and triplet states.The contributing states are tentatively identified.
FLASH THERMOLYSIS OF FUNCTIONALISED PHOSPHIRANES
Haber, Steffen,Floch, Pascal Le,Mathey, Francois
, p. 225 - 228 (2007/10/02)
A series of functionalized parent phosphiranes are prepared from the 1-chloro compound.The thermolysis of 1-alkenyl-phosphiranes at 700 deg C produces phosphaalkynes via the rearrangement of vinylphosphinidenes.Methylidynephosphine is obtained by thermolysis of cyclopropylphosphirane.
PRINCIPLES OF PHOSPHORUS CHEMISTRY
Bock, Hans
, p. 3 - 53 (2007/10/02)
An up-to-date concept of bonding in phosphorus compounds has to be based on the reality of molecular states.Molecules, which change their structure with energy, at present are best rationalized in terms of topology and symmetry, effective nuclear potentials and charge distribution.To reduce the complexity of the resulting manifold, comparison of equivalent states of chemical calculations, is strongly recommended.Adding the time-scale, molecular dynamics within the numerous degrees of freedom become important, also as a basis to gain some understanding og the rather complex microscopic reaction pathways of medium-sized molecules.Examples are presented to illustrate the use of spectroscopic "fingerprints" for the analysis and optimization of gasphase reactions as well as the benefit of inherent information on molecular states for the preparative phosphorus chemist.The catalytic dehydrochlorination of alkyldichlorophosphanes RH2C-PCl2 -> RHC=PCl -> R-CP and their dechlorination on magnesium metal surface are discussed in some detail as well as the generation of other unsaturated phosphorus molecules like Cl-P=O, Cl-P=S, ClP(=O)2, Cl-P(=S)2 or H3C-P=CH2.Approximate energy hypersurface calculations for the gasphase equilibrium P4 = 2P2 or for the unexpected dehydration (H3C)2HP=O -> H2O + H3C-P=CH2, which includes chemical activation, provide some insight into microscopic reaction pathways of phosphorus compounds.
