Tripodal Amides Containing a Totally Silicon‐Based Ligand Framework

Abstract
A novel type of tripodal amido ligand with a totally siliconbased (trisilylsilane‐derived) ligand framework has been synthesized and coordinated to tetravalent titanium and zirconium. The key compound in the ligand synthesis is the chlorosilane H3CSi{Si(CH3)2CI}3 (2) which upon condensation with a range of primary amines R‐NH2 (R = aryl, alkyl) yields the amino‐functionalized ligand precursors H3CSi{Si(CH3)2NHR}3 (3a–e). Their corresponding trilithium salts have been found to be the appropriate amide transfer reagents in the subsequent syntheses of the transition metal complexes. Single‐crystal X‐ray structure analyses of the trilithium triamide H3CSi{Si(CH3)2N(Li)tBu}3 (4a) and the Ti complex H3CSi{Si(CH3)2N(p‐Tol)}3TiBr (5b) have established their respective adamantane‐ and [2.2.2]bicyclooctane‐related cage structures.

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