Abstract

In a 2:2 reaction with silver(I) chloride or bromide, 1,5‐bis(1‐phospholano)pentane (1a) afforded frame‐like macrocyclic structures, with intra‐ (2, Cl) or intermolecular (3, Br) halido bridges. In contrast, 1,7‐bis(1‐phospholano)heptane (1b) formed coordination polymers 4a (Cl) and 4b (Br) with bridging bis‐phospholane and halido ligands. A unique paddle wheel‐type metallacryptand structure 5 was obtained from 1a and silver(I) bromide in a 2:3 reaction (M:L). All complexes were fully characterized by NMR, IR spectroscopy, mass spectrometry, and X‐ray crystallography.

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