Generation and Ionization Pattern of the Iso(valence)electronic Compounds CIP(O)₂ and CIP(S)₂

Abstract

The title compounds may be regarded as a missing link in the series of planar 24‐electron compounds Cl3B, Cl2CS, ClPS2, ClPO2, C1NO2, SO3. They are readily accessible by dissociation of betaine 1. The electron distribution in the compounds of this series is discussed on the basis of PE spectra. The positively charged centers are surrounded in a starlike fashion by substituents that are mostly negatively charged (X  O, S).

Sulfenic Acids in the Gas Phase: A Photoelectron Study

“…In the latter case, digital subtraction of a prerecorded spectrum of isobutene unmasks the ionization pattern of the sulfenic acids 1 and 4 or of their isomerization or decomposition products. Such a procedure has already proven valuable for the PE caracterization of short-lived species such as ClPS 2 , 17 FPS 2 and FPS, 18 and N-cyanomethanimine, 19 among others.…”

New perthiophosphonic acid anhydrides and the direct indication of the dimer‐monomer equilibrium. NMR and X‐Ray Studies

“…On the other hand, with the sterically demanding substituent c, only the monomer 2c occurs [5]. The formation of 2a starting from la has already been proved in gaseous phase by heating la in vacuuni [6].…”

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO2P Source

“…have generated considerable scientific interest due to their potential as phosphorylation/phosphonylation reagents − as well as their participation as intermediates/final products of combustion reactions involving warfare agents and flame retardants. , Dioxyphosphorane ( 1 , Figure ) and cis / trans -alkoxyphosphanone ( 2 , 3 ) are the structural isomers that these molecules are capable of adopting. The former, formally a P­(V) species, is thermodynamically more favorable for all species regardless of the nature of the R substituent − ,− with the exception of the parent compound (i.e., R = H). − In fact, parent dioxophosphorane 1a has been predicted to be more than 40 kJ/mol less stable than the cis-isomer of hydroxyphosphanone ( 2a ), − and it was then not surprising that this least thermodynamically stable isomer (i.e., HPO 2 ) was only recently detected via infrared spectroscopy among several products formed during 193/266 nm laser photolysis of 2a in the Ar matrix at 2.8 K …”

“…Dioxophosphoranes are usually stabilized within a larger molecular framework and are, in some instances, deliberately released for detection/identification as well as further reactivity studies such as in the case of compounds 4 through 7 (Figure ). In fact, owing to the exceptional electrophilic characteristic of the three-coordinate phosphorus atom, the identity of dioxophosphoranes was normally established by either low-temperature matrix isolation procedures, − , high-temperature gas-phase analysis, intramolecular C–H/C–F bond activations, , or trapping experiments, that is, reactivity studies in the presence of, for example, alcohols, amines, or epoxides . The reactivity of transient dioxophosphoranes with different molecules actually represents a very useful approach for the phosphorylation/phosphonylation of organic molecules potentially yielding compounds, including the biologically important ones, that would be difficult to obtain by other synthetic methods. − For example, fragmentation of compounds that resemble 4 (Figure ) represents arguably the most versatile/valuable approach in generating synthetically usable RO 2 P fragments. ,, On the other hand, base-stabilized compounds such as 9 and 10 ( 8 is in fact produced by the photolysis of 4 at −75 °C in THF), including transition metal-stabilized RPO 2 complexes, are generally not reported to act as a source of the RO 2 P fragment that could be used for further reactivity studies. ,,− A similar conclusion could be reached for neutral but zwitterionic ( 11 , Figure ) − and anionic ( 12 ) − compounds (i.e., the O-deprotonated form of the monobasic tautomer of phosphonous acid) because they could be viewed as parent dioxophosphorane-containing species.…”