2020
DOI: 10.1021/acs.inorgchem.0c01934
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Synthesis of Sterically Demanding Secondary Phosphides and Diphosphanes and Their Utilization in Small-Molecule Activation

Abstract: Sterically demanding secondary potassium phosphides (4) were synthesized and investigated. Reaction with halophosphanes (5) yields diphosphanes (6), whereas reaction with CS 2 yields phosphanyl dithioformates (10). These can be further converted to the corresponding phosphanyl esters of dithioformic acid R 2 P−C(S)S−PR 2 (8). One of these thioesters (8) was found to undergo a migration reaction, resulting in the formation of a phosphanylthioketone with an additional phosphanylthiolate group ( 9), which was use… Show more

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Cited by 14 publications
(60 citation statements)
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“…1.658(1) Å, Table 1). [49] This bond elongation can be attributed to the population of the antibonding π* orbital with one electron in 2_K (see IR spectra of 1 and 2_K, Figure S6; as well as Figure S7) and has been reported for analogous ketyl derivatives before. [5,11] This structural change of the CÀ S bond upon reduction is also manifested in the IR spectrum.…”
supporting
confidence: 59%
“…1.658(1) Å, Table 1). [49] This bond elongation can be attributed to the population of the antibonding π* orbital with one electron in 2_K (see IR spectra of 1 and 2_K, Figure S6; as well as Figure S7) and has been reported for analogous ketyl derivatives before. [5,11] This structural change of the CÀ S bond upon reduction is also manifested in the IR spectrum.…”
supporting
confidence: 59%
“…Die Synthese der Alkalimetallsalze des neuen Thioketylradikalanions begann mit der Darstellung des Thioketons 1 (siehe Hintergrundinformationen), [49] welches zwei sterisch anspruchsvolle Phosphanylsubstituenten besitzt ( i Pr und Ter‐Gruppen; Ter=Terphenyl=2,6‐bis‐(2,4,6‐trimethylphenyl)phenyl [50] ). Die Radikalverbindungen 2 _ K und 2 _ Na wurden daraufhin bei Raumtemperatur in THF in einem SET‐Reduktionsschritt aus dem Edukt 1 unter Verwendung von KC 8 oder eines metallischen Na‐ bzw.…”
Section: Methodsunclassified
“…1.658(1) Å, Tabelle 1). [49] Diese Bindungsaufweitung kann auf die Population des antibindenden π*‐Orbitals mit einem Elektron in 2 _ K zurückgeführt werden (siehe auch IR‐Spektren von 1 und 2 _ K , Abbildungen S6 und S7). Dies wurde zuvor bereits für analoge Ketylderivate berichtet [5, 11] .…”
Section: Methodsunclassified
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“…Among potential coupling products, diphosphanes have received attention as both synthetic targets as well as undesired by-products, for example in the synthesis of tertiary phosphines. [12][13][14][15][16][17] Diphosphanes have also been shown to readily react with alkenes and alkynes to give diphos-type ligands. 13 Classically, tetraorganodiphosphanes have been synthesized through Wurtz-type reductive coupling of R 2 PCl using various metals (Li, Na, K, Mg and Hg) (Scheme 1, I).…”
Section: Introductionmentioning
confidence: 99%