Gasphasen‐Reaktionen, 85^[1] Darstellung und Photoelektronen‐Spektrum von Ethyldithioxo‐λ⁵‐phosphoran H₅C₂‐P(=S)₂

Abstract

Gas-Phase Reactions, 85 [l]. -Preparation and Photoelectron Spectrum of Ethyldithioxo-i5-phosphorane H5C2 -P( = S),The first alkyldithioxo-h5-phosphorane 1 a is obtained by selective monomerization of its readily accessible dimer, 2,4-diethyl-1,3,2h5,4h5-dithiadiphosphetane-2,4-dithione [4 (R = ogen derivatives FPS2 (1 b) and CIPSz (1 c).C,H,)], at 970K in the gas phase and characterized by its photoelectron spectrum, which is assigned by both Koopmans' correlation and radical-cation state comparison with the halZu der rasch anwachsenden Zahl von Verbindungen, die durch Mehrfach-Bindungen zwischen Nichtmetall-Elementen der dritten und hoherer Perioden den Geltungsbereich der klassischen Doppelbindungsregel zunehmend einschranken, gehoren als Prototypen auch die 03h5-Dithioxophosphorane 1 [31. Sie konnten durch raumerfiillende Gruppen kinetisch stabilisiert { 1 [R = 2,4,6-(t-C4H9)3C6H2]} [3-61 oder als monomeres Trithiometaphosphat-Salz 2L3%71 in Substanz isoliert werden, und ihre reaktiven, vieratomigen HalogenDerivate lieBen sich durch thermische Gasphasen-Dissoziation der entsprechenden Pyridinium-Betaine 3 unter angenahert unimolekularen Bedingungen erzeugen und photoelektronen-spektroskopisch charakterisieren ['s8I [Gl. (l)]. sollte zeigen, ob das Gleichgewicht (2) in der Gasphase unter angenahert unimolekularen Bedingungen auf der Seite des Monomeren liegt und so erstmals ein alkyliertes 03h5-Dithioxophosphoran 1 mittlerer MolekulgroBe nachgewiesen werden kann.

Ionization Potentials of Silenes (R‘2SiCR2). Experiment and Theory

“…The PE spectra were digitally recorded and processed. Gas-phase thermolysis of disilacyclobutane 6 was executed in the internal electron collision furnace 14 of the PE spectrometer. The thermolysis equipment was released from chemisorbed water in the system first by heating the system to 800 K, and then a PE spectrum of the 6 as a purity check was registered.…”

“…The PE spectra of 6 and 3 were obtained by heating the sample up to 400 K (Figure 1A and Figure 2). The temperature of the electron collision furnace 14 was increased in intervals of 50 K. At 870 K furnace temperature, only the PE spectrum of the pyrolysis product of 4 was recorded (Figure 1B).…”

Pyrimidin‐/thiazol‐/thiazolin‐ylidenamidothiophosphoric dichlorides

“…Dichlorothiophosphorus(V) derivatives have found a significant place in literature [1] as versatile synthons for obtaining a wide variety of important organophosphorus compounds ranging from deoxynucleoside/nucleotide esters [2][3][4], phosphorus containing crown ethers [5,6], functionalized phosphorus macrocycles [7], dithioxo-5 -phosphorane [8], thiophosphoramide esters having flame retardant properties [9] to the compounds having insecticidal and nematocidal properties [10][11][12][13]. A number of methods for the sulfurization of dichlorophosphorus(III) compounds to form dichlorothiophosphorus (V) compounds are available in literature.…”