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Unexpected Isomerization of Hexa-tert-butyl-octaphosphane.

ABSTRACT: Octaphosphane {cyclo-(P₄ tBu₃ )}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-?P³ )], 3) and a dinuclear complex ([(AuCl)₂ (2-?P³ ,?P^3' )], 4). With cis-[PdCl₂ (cod)] (cod=1,5-cyclooctadiene), the chelate complex ([PdCl₂ (2-?² P² ,P^2' )], 5) with a different coordination mode of the ligand was obtained.

SUBMITTER: Grell T

PROVIDER: S-EPMC7027762 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Unexpected Isomerization of Hexa-tert-butyl-octaphosphane.

Grell Toni T Hey-Hawkins Evamarie E

Chemistry (Weinheim an der Bergstrasse, Germany) 20191227 5

Octaphosphane {cyclo-(P4 tBu3 )}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 behavi ...[more]

PMID: 31758612

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