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

Reactions of cuprous chloride with the phosphorus–nitrogen cage ligand 2,4,6,8,9,10-hexamethyl-2,4,6,8,9,10-hexaaza-1,3,5,7-tetraphosphaadamantane, P4(NCH3)6, in acetonitrile form distinct solids depending on the ligand-to-metal ratio. Three structurally characterized compounds include: a solvated 3-D network of formula [P4(NCH3)6]2(CuCl)3(CH3CN)2; a “ladder-type” polymer {[μ2-P4(NCH3)6]2(CuCl)2}∞; and a monomeric complex [P4(NCH3)6]2CuCl. Thermal decomposition of the solvated network results in formation of two more materials [P4(NCH3)6]2(CuCl)3, and [P4(NCH3)6](CuCl)2 that are not isolated from solution reactions. The variety of products isolated based solely on ligand-to-metal ratio suggest that this system participates in solution equilibria common to many phosphorus(III) ligands and multiple solubility equilibria.

Graphical abstractThe adamantane shaped ligand P4(NCH3)6 reacts with CuCl in acetonitrile to form multiple products. Structurally characterized compounds include a monomer (shown), a linear polymer and a three-dimensional network.Figure optionsDownload full-size imageDownload as PowerPoint slide