The Self‐Assembly of Ag^I‐Containing Heterobimetallic Complexes with a Discriminatory N,P‐Based Heteroditopic Ligand

Abstract

The heteroditopic ligand L1, which contains discriminatory N‐based pyrimidine‐hydrazone‐pyridine (pym‐hyz‐py) and hybrid N,P‐based pym‐hyz‐phosphole coordination sites, reacts with AgI triflate to give a dimeric [AgL1]2(SO3CF3)2 complex in which the AgI ions are bound to donors of both coordination sites. Unusual heterobimetallic complexes could also be reliably formed in one pot reactions with L1 and combinations of AgI and either ZnII, PbII or CuII triflate. Here, the coordination sites of L1 proved discriminatory, as the AgI ions were consistently only bound by the hybrid N,P‐coordination site, with the second metal occupying the other site. The solid‐state structures of the dimeric complexes [AgL1]2(SO3CF3)2, [AgZnL1(SO3CF3)3]2 and [AgPbL1(SO3CF3)3]2 show structural diversity; they contain L1 molecules in different conformations, AgI ions in a variety of coordination geometries, as well as argentophilic contacts.