Bis(amido)diazadiarsetidinide and Amido(imino)arsenide Complexes of Divalent Metals. Issue 48 (30th November 2021)

• Record Type: Journal Article
• Authors: Ritter, Christian; von Hänisch, Carsten
• Is Part Of: European journal of inorganic chemistry. Issue 48(2021)
• Page Start: 5103
• Page End: 5111
• Publication Date: 2021-11-30
• Subjects: Amido(imino)arsenide -- Diazadiarsetidine -- Pnictogen -- Tetrylene -- Triaminoarsine; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202100832
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The Mg and Ca complexes of the tert ‐butyl substituted bis(amido)diazadiarsetidinides [{( t BuNAs)2 ( t BuN)2 }M(thf)2 ] (M=Mg (1 ), Ca (6 )) were prepared by addition of n Bu‐ sec BuMg or [{( p ‐ t Bu)(C6 H4 )CH2 }2 Ca] to [( t BuNAs)2 ( t BuNH)2 ] (Ia ). Upon evaporation of coordinating THF, 1 is selectively converted to the amido(imino)arsenide complex [Mg{As(N t Bu)2 }2 ] (2 ) whereas 6 decomposes to several products under these conditions. Hydrolysis of 2 with H2 O yields the hitherto unknown compound As(NH t Bu)3 (3 ) whereas hydrolysis of Ia leads to the formation of the oxygen bridged bis(amidodiazadiarsetidine) [O{( t BuNH)( t BuNAs)2 }2 ] (4 ). Reaction of 2 with 3 yields the heteroleptic Mg complex with an amido(imino)arsenide and a bis(amido)diazadiarsetidinide ligand [{( t BuNAs)2 (NH t Bu)(N t Bu)}Mg{As(N t Bu)2 }] (5 ). The homologous Ca compound (7 ) was obtained by conversion of Ia with Ca(hmds)2 (hmds=N(SiMe3 )2 ). Finally, the tetrylene complexes [E{( t BuNAs)2 ( t BuN)2 }] (E=Ge (8 ), Sn (9 ), Pb (10 )) were prepared by either conversion of Ia with E(hmds)2 for E=Sn, Pb or by addition of the dichlorides of Ge and Sn to [( t BuNAs)2 ( t BuNLi)2 ] (Ib ). All compounds were characterised by NMR and IR spectroscopy, mass spectrometry and single crystal x‐ray diffraction for 1, 2, 4, 5, 6 and 10 . Abstract : Monomerisation of a cyclic bis(amido)diazadiarsetidinide ligand to an allylic amido(imino)arsenide ligand in the coordination sphere of magnesium is described. Moreover, the transfer of these ligands to calcium as well as germanium, tin and lead is described. From these investigations also heteroleptic complexes were obtained, showing the bis(amido)diazadiarsetidinide and the amido(imino)arsenide ligand.