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Structure and Reactivity of Alkaline Metal Bis(amido)diazadiarsetidinides
Author(s) -
Ritter Christian,
Bergunde Jakob,
Weigend Florian,
Hänisch Carsten
Publication year - 2021
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202100214
Subject(s) - chemistry , medicinal chemistry , protonation , reactivity (psychology) , intramolecular force , moiety , stereochemistry , metal , ion , organic chemistry , medicine , alternative medicine , pathology
A series of alkaline metal functionalised tert ‐butyl substituted bis(amido)diazadiarsetidinides [( μ ‐N( t Bu)As) 2 (N( t Bu)M) 2 ] (M=K ( 1 ), Rb ( 2 ), Cs ( 3 ), Na⋅thf ( 4 ), Na ( 5 )) were prepared and their solid state structures investigated in detail. Further substitution reactions with tert ‐butyl substituted element chlorides of P, As, Sb and Bi were performed. The conversion of two equivalents t Bu 2 AsCl ( II ) with 1 – 3 unexpectedly leads to the introduction of only one arsine moiety ([( μ ‐N( t Bu)As) 2 (N( t Bu)H)(N( t Bu)As t Bu 2 ] ( 6 )) while the other nitrogen atom gets protonated by ether cleavage. The reaction of one equivalent t BuECl 2 (E=As ( III ), Sb ( IV )) with 1 , 2 or 3 yielded the intended cage compounds [( μ‐ N( t Bu)As) 2 (N t Bu) 2 E t Bu] (E=As ( 7 ), Sb ( 8 )) in high yields. Reaction of 1 – 3 with two equivalents of t Bu 2 E'Cl (E’=Sb ( V ), Bi ( VI )) yields the twofold substituted bis(amido)diazadiarsetidines [( μ‐ N( t Bu)As) 2 (N( t Bu)E’ t Bu 2 ) 2 ] (E’=Sb ( 9 ), Bi ( 10 )), which show weak intramolecular E’–E’ interactions.