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Updated: May 1, 2026

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
A tripodal benzylene-linked trisamidophosphine ligand scaffold: synthesis and coordination chemistry with group(IV)
Sonja Batke1, Malte Sietzen, Hubert Wadepohl
1Anorganisch-Chemisches Institut, Universität Heidelberg , Im Neuenheimer Feld 276, 69120 Heidelberg, Germany.
Abstract:
A new tripodal trisamidophosphine ligand (1) based on the trisbenzylphosphine backbone has been synthesized in three steps starting from NaPH2 and phthaloyl-protected 2-aminobenzyl bromide. At elevated temperatures, 1 reacts directly with M(NMe2)4 (M = Zr, Hf) to afford the dimethylamido complexes [PN3]M(NMe2) (M = Zr, Hf) (2), which are easily converted into the corresponding triflates [PN3]MOTf (M = Zr, Hf) (3) via reaction with triethylsilyl trifluoromethanesulfonate. The related titanium chloro complex [PN3]TiCl (4-Ti) is obtained from 1 and Bn3TiCl via protonolysis. Triple deprotonation of 1 with n-butyllithium affords the tris-lithium salt Li3[PN3] (1-Li), which serves as a common starting material for the preparation of all the group(IV) chlorides [PN3]MCl (M = Ti, Zr, Hf) (4). Upon treatment of 4-Ti with Bn2Mg(thf)2, formation of a benzyltitanium species is observed, which is converted cleanly into a ligand-CH-activated species (5-Ti).
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