A Modular Approach to Inorganic Phosphazane Macrocycles. (21st April 2017)

• Record Type: Journal Article
• Authors: Plajer, Alex J.; García‐Rodríguez, Raúl; Benson, Callum G. M.; Matthews, Peter D.; Bond, Andrew D.; Singh, Sanjay; Gade, Lutz H.; Wright, Dominic S.
• Is Part Of: Angewandte Chemie. Volume 129:Number 31(2017)
• Page Start: 9215
• Page End: 9218
• Publication Date: 2017-04-21
• Subjects: Makrocyclen -- Modulare Synthese -- Phosphazane -- Röntgenstrukturanalyse; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201702558
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Inorganic macrocycles, based on non‐carbon backbones, present exciting synthetic challenges in the systematic assembly of inorganic molecules, as well as new avenues in host–guest and supramolecular chemistry. Here we demonstrate a new high‐yielding modular approach to a broad range of trimeric and hexameric S‐ and Se‐bridged inorganic macrocycles based on cyclophosphazane frameworks, using the building blocks [S=(H)P(μ‐NR)]2 . The method involves the in situ generation of the key intermediate [E . . . . . _ (S . . . . . _ )P(μ‐NR)]2 2− (E=S, Se) dianion, which can be reacted with electrophilic [ClP(μ‐NR)]2 to give P III /P V hexameric rings or reacted with I2 to give trimeric P V variants. Important issues which are highlighted in this work are the competitive bridging ability of S versus Se in these systems and the synthesis of the first air‐stable and chiral inorganic macrocycles.