2019
DOI: 10.1002/chem.201904531
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Unexpected Isomerization of Hexa‐tert‐butyl‐octaphosphane

Abstract: Octaphosphane {cyclo-(P 4 tBu 3 )} 2 (1)u ndergoes an unexpected isomerization reactiontothe constitutional isomer 2,2',2'',2''',3,3'-hexa-tert-butyl-bicyclo[3.3.0]octaphosphane (2)i nt he presence of Lewis acidicm etal salts. The mechanism of this reactioni sd iscussed and elucidated with DFT calculations. The resultsu nderline the fascinating similarity between phosphorus-rich and isolobal carbon compounds. The new bicyclic octaphosphane 2 shows ad ynamic behavior in solution and reacts with [AuCl(tht)] (tht… Show more

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Cited by 9 publications
(14 citation statements)
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“…The Au-P bond lengths in both polymorphs (2.231(1) Å-2.239(1) Å) are in the range of similar complexes. 5,6,[30][31][32] The P-P bond lengths (2.192(2) Å-2.226(2) Å) are also in the expected range. 33 In accordance with the molecular structure observed in the solid state, the 31 P{ 1 H} NMR spectrum of 1 (Fig.…”
Section: Resultsmentioning
confidence: 66%
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“…The Au-P bond lengths in both polymorphs (2.231(1) Å-2.239(1) Å) are in the range of similar complexes. 5,6,[30][31][32] The P-P bond lengths (2.192(2) Å-2.226(2) Å) are also in the expected range. 33 In accordance with the molecular structure observed in the solid state, the 31 P{ 1 H} NMR spectrum of 1 (Fig.…”
Section: Resultsmentioning
confidence: 66%
“…The oligodentate ligand {cyclo-(P 4 t Bu 3 )} 2 18 can bind up to three gold(I) chloride fragments. 5,6 Furthermore, we have observed a distinct intramolecular dynamic behaviour of the corresponding gold(I) complexes as well as an exchange of gold(I) chloride fragments between different oligonuclear complexes, suggesting the pres-ence of equilibria. Therefore, it was interesting to see whether smaller cyclooligophosphanes also display such a dynamic intermolecular behaviour.…”
Section: Introductionmentioning
confidence: 71%
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