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Unexpected Isomerization of Hexa‐ tert ‐butyl‐octaphosphane
Author(s) -
Grell Toni,
HeyHawkins Evamarie
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201904531
Subject(s) - isomerization , chemistry , tetrahydrothiophene , hexa , bicyclic molecule , medicinal chemistry , ligand (biochemistry) , lewis acids and bases , stereochemistry , coordination complex , metal , catalysis , organic chemistry , biochemistry , receptor
Octaphosphane { cyclo ‐(P 4 t Bu 3 )} 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 ‐κ P 3 )], 3 ) and a dinuclear complex ([(AuCl) 2 ( 2 ‐κ P 3 ,κ P 3′ )], 4 ). With cis ‐[PdCl 2 (cod)] (cod=1,5‐cyclooctadiene), the chelate complex ([PdCl 2 ( 2 ‐κ 2 P 2 , P 2′ )], 5 ) with a different coordination mode of the ligand was obtained.