Octaphosphane {cyclo-(P4tBu3)}2 (1) undergoes an unexpected isomerization reaction to the constitutional isomer 2,2′,2′′,2′′′,3,3′-hexa-tert-butyl-bicyclo[3.3.0]octaphosphane (2) in the presence of Lewis acidic metal salts. The mechanism of this reaction is discussed and elucidated with DFT calculations. The results underline the fascinating similarity between phosphorus-rich and isolobal carbon compounds. The new bicyclic octaphosphane 2 shows a dynamic behavior in solution and reacts with [AuCl(tht)] (tht=tetrahydrothiophene) to give a mono- ([AuCl(2-κP3)], 3) and a dinuclear complex ([(AuCl)2(2-κP3,κP3′)], 4). With cis-[PdCl2(cod)] (cod=1,5-cyclooctadiene), the chelate complex ([PdCl2(2-κ2P2,P2′)], 5) with a different coordination mode of the ligand was obtained.

Unexpected Isomerization of Hexa-tert-butyl-octaphosphane / T. Grell, E. Hey-Hawkins. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - 26:5(2020 Jan 22), pp. 1008-1012. [10.1002/chem.201904531]

Unexpected Isomerization of Hexa-tert-butyl-octaphosphane

T. Grell
Primo
;
2020-01-22

Abstract

Octaphosphane {cyclo-(P4tBu3)}2 (1) undergoes an unexpected isomerization reaction to the constitutional isomer 2,2′,2′′,2′′′,3,3′-hexa-tert-butyl-bicyclo[3.3.0]octaphosphane (2) in the presence of Lewis acidic metal salts. The mechanism of this reaction is discussed and elucidated with DFT calculations. The results underline the fascinating similarity between phosphorus-rich and isolobal carbon compounds. The new bicyclic octaphosphane 2 shows a dynamic behavior in solution and reacts with [AuCl(tht)] (tht=tetrahydrothiophene) to give a mono- ([AuCl(2-κP3)], 3) and a dinuclear complex ([(AuCl)2(2-κP3,κP3′)], 4). With cis-[PdCl2(cod)] (cod=1,5-cyclooctadiene), the chelate complex ([PdCl2(2-κ2P2,P2′)], 5) with a different coordination mode of the ligand was obtained.
gold; isomerization; oligophosphanes; palladium; phosphorus
Settore CHIM/03 - Chimica Generale e Inorganica
27-dic-2019
Article (author)
File in questo prodotto:
File Dimensione Formato  
Chemistry A European J - 2019 - Grell - Unexpected Isomerization of Hexa‐tert‐butyl‐octaphosphane.pdf

accesso aperto

Tipologia: Publisher's version/PDF
Dimensione 760.7 kB
Formato Adobe PDF
760.7 kB Adobe PDF Visualizza/Apri
Grell_et_al-2019-Chemistry_-_A_European_Journal.sup-1.pdf

accesso aperto

Descrizione: Supporting information
Tipologia: Altro
Dimensione 1.94 MB
Formato Adobe PDF
1.94 MB Adobe PDF Visualizza/Apri
chem.201904531_Accepted Article_AAM.pdf

accesso aperto

Descrizione: file ad accesso apterto con embargo fino al 22/11/2020
Tipologia: Post-print, accepted manuscript ecc. (versione accettata dall'editore)
Dimensione 370.22 kB
Formato Adobe PDF
370.22 kB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/906721
Citazioni
  • ???jsp.display-item.citation.pmc??? 1
  • Scopus 6
  • ???jsp.display-item.citation.isi??? 6
social impact