Aggregation, Reaggregation and Degradation of a Trifunctional Thallium(I) Amide Induced by Weak TlI TlI Attraction

Metal exchange of the solvated tripodal lithium amide [H 3 CC{CH 2 N(Li‐solv)SiMe 3 } 3 ] ( 1 , solv = ether solvent) with thallium(I) chloride leads to the previously reported pentametallated dimeric thallium amide [{H 3 CC(CH 2 NSiMe 3 ) 3 } 2 (H)Tl 5 ] ( 2 ) in high yield. That the redox‐induced partial demetallation of the amide presumably occurs at an intermediate stage of the metal exchange is inferred from the isolation and structural characterization of the mixed Tl‐Li amide [H 3 CC{CH 3 N(Tl) SiMe 3 } 3 ][H 3 CC{CH 2 NSiMe 3 } 3 (H)(Tl)(Li‐thf)]·(toluene) ( 3 ), which has a crystal structure closely related to that of 2 . In both cases the central structural motif, defined by weakly attractive Tl ⃛ Tl contacts, is a tetrahedral metal array in which a triangular thallium triamide unit is capped by an exposed Tl atom of a second building block. Compound 3 may be converted to 2 by metal exchange with TlCl. The two supramolecular components of 2 reaggregate upon recrystallization in a nonpolar solvent such as pentane to yield the dimeric aggregate of the fully metallated thallium amide [H 3 CC{CH 2 N(Tl)‐SiMe 3 } 3 ] 2 ( 4 ). An X‐ray crystallographic study of 4 established the existence of dimeric aggregation through Tl ⃛ Tl interactions leading to a more open dimeric form than 2 and 3 , which is interpreted as being due to a structural mismatch of the building blocks. Compound 4 may be thermally degraded by prolonged stirring in toluene at ambient temperature to yield the previously reported mixed‐valence Tl I Tl II amide [H 3 CC(CH 2 NSiMe 3 ) 3 Tl 2 ] ( 5 ).