Synthesis and crystal structures of coordination polymers, networks and complexes of an adamantane shaped phosphorus–nitrogen cage ligand and cuprous chloride

A growing family: New structures of coordination polymers containing adamantane-shaped phosphorus–nitrogen cage ligands

“…Recent work has shown that P-N compounds also display interesting macrocyclic structures and form extended structures with metal ions to make their own types of coordination polymers and networks [1][2][3][4][5]. A long-known reaction of phosphorus trichloride with methylamine yields the adamantane shaped cage molecule shown in Scheme 1.…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[P4(NMe)6], CuCl / MeCN, 2 days T [526] [H2Ta(tdci)2]CI3 (930) TaCl5, tdci / MeOH J [527] [H11Ta7O12(tdci)6] (931)…”

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

“…Sommer reported the reaction of lithiated benzylamine, LiHNCH 2 Ph, with PCl 3 , as a viable route to 1Bn (Figure 5a). 81,82 Recently we have reported chlorosilane elimination as an alternative to dehydrochlorination or salt elimination. 83 Specifically, bis-silylated amines RN(SiMe 3 ) 2 (R = Me, n Bu, CH 2 Ph, and CH 2 CH�CH 2 ) react smoothly with PCl 3 in a 6:4 amine:phosphine stoichiometry to eliminate volatile Me 3 SiCl and form derivatives of 1R in 50−95% yields on gram scales (Figure 5a).…”

“…89−91 Oxidation of Tetrahedral of Linear PN Cages to Make Robust Covalent Monomers. While the P(III) vertices of these cages readily form coordination polymers, 81,82 they are not suited for making covalently bonded polymers or networks without further modification. We envisioned that oxidizing the P(III) vertices with Me 3 SiN 3 (Staudinger reaction) to form silyl-phosphinimine vertices would allow us to use PN cages as poly nucleophiles based on the high polarization of the Si−N bonds (Figure 5c).…”