Notizen: Beiträge zur Chemie des Phosphors, 77¹ Spektroskopischer Nachweis eines Diphosphirans (Diphosphacyclopropans) / Contributions to the Chemistry of Phosphorus, 77¹ Spectroscopic Detection of a Diphosphirane (Diphosphacyclopropane)

Abstract

<jats:p>1,2 - Diphenyl - 3,3 - dimethyl - diphosphirane (1,2- Diphenyl- 3,3- dimethyl-diphosphacyclopropane) (1) is formed by the reaction of K(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)P–P(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)K with 2,2-dichloropropane in n-pentane at —30 °C. It could be detected and identified by its <jats:sup>31</jats:sup>P NMR singlet at —122 ppm, which lies in the high field region characteristic for phosphorus three-membered ring compounds, as well as by its mass spectrum. Besides, (PC<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>5</jats:sub> and several cyclocarbaphosphanes of ring sizes five and six are formed. After the reaction of (CH<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>Si(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)P–P(C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>)Si(CH<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub> with methylene iodide a weak <jats:sup>31</jats:sup>P NMR signal at —147 ppm could be observed, which probably corresponds to the 1,2-diphenyl-diphosphirane.</jats:p>

Selective Reductions of N,N‐Bis{chloro(aryl)‐phosphino}‐amines Yielding Three‐, Five‐, Six‐, and Eight‐Membered Cyclic Azaphosphanes

“…The reduction of 1 b with KC 8 led to a new compound, which selectively gives an AMX pattern in the 31 P NMR spectrum, with two double doublets at 59.5 and 74.1 ppm as well as a pseudo triplet at 130.2 ppm. In combination with the CI (isobutane) mass spectrum, where a signal at m / z 518 could be detected and a former publication by Baudler et al., a hint for the formation of another cyclic compound, 6 , could be gained; compound 6 is another five‐membered cycle containing three phosphorus and two nitrogen atoms (Scheme ). As the AMX spin system implies the existence of three different phosphorous species, the phenyl groups on the neighboring phosphorous atoms must be in trans positions to each other.…”

PhP=CPh2 and Related Phosphaalkenes: A Solution Equilibrium between a Phosphaalkene and a 1,2‐Diphosphetane

“…We speculate that this compound is diphosphirane 3a . For comparison, similar species, 3,3‐dimethyl‐1,2‐diphenyldiphosphirane and 3,3‐diphenyl‐1,2‐disupermesityldiphosphirane, are known with reported 31 P chemical shift of –122 ppm and –74 ppm, respectively , . The 13 C{ 1 H} NMR spectrum of the hexanes‐soluble fraction containing 3a showed resonances that may be attributable to the ring carbon in diphosphirane 3a [ δ = 55.6 (t), 1 J CP = 49 Hz] and to unreacted Ph 2 C O ( δ = 196.6).…”

Beiträge zur Chemie des Phosphors, 80 [1] Über die Phosphor-Bor-Dreiringverbindung (t-BuP)2BN(i-Pr)2 / Contributions to the Chemistry of Phosphorus, 80 [1] About the Phosphorus Boron Three-Membered Ring Compound (t-BuP)2BN(i-Pr)2

“…Hinsichtlich der Bindungsverhältnisse im P2B-Ring von 1 ergibt sich aus der Hochfeldlage der chemischen Verschiebung im 31 P-NMR-Spektrum, die mit der anderer phosphorhaltiger monocyclischer Dreiringverbindungen [5,6,17,18,[23][24][25] …”