Preorganized Ag^I Bimetallic Precursor with Labile Diphosphorus Ligands for a Programmed Synthesis of Organometallic–Organic Hybrid Polymers

Abstract

An AgI dimer capped with labile organometallic diphosphorus ligands [Cp2Mo2(CO)4(η2‐P2)] (Cp=C5H5) acts as a highly pre‐organized molecular precursor to direct the construction of 1D or 2D, and 3D organometallic–organic hybrid coordination polymers upon reaction with ditopic pyridine‐based linkers. The formation of the supramolecular aggregates can be controlled by the stoichiometry of the organic molecules, and the mechanism is supported by DFT calculations.

Organometallic–Organic Hybrid Polymers Assembled from Pentaphosphaferrocene, Bipyridyl Linkers, and CuI Ions

“…Most recently, we also reported the first series of neutral 2D CPs based on pentaphosphaferrocene ( 1 ), CuCl and ditopic pyridine‐based linkers. [8a] Based on these results, the question arises as to whether it is possible to further enrich this library of hybrid CPs with new neutral and cationic compounds with unprecedented topologies. Herein, we report the reaction of pentaphosphaferrocene ( 1 ) with Cu I salts of the anions [BF 4 ] – and [PF 6 ] – or the coordinating anion Br – in the presence of the ditopic organic linkers 4,4′‐bipyridine ( 2 ) or trans ‐1,2‐di(pyridine‐4‐yl)ethene ( 3 ).…”

Novel synthetic route towards heteroleptic pnictogen-rich organometallic–inorganic coordination compounds

“…16 Interestingly, the η 2 -coordinated ligands A are, in contrast to the η 1 :η 1 -coordinated ones, rather labile and can thus be readily substituted with stronger donor ligands such as pyridine-based organic molecules. 17 Therefore, we came up with the idea of studying whether those labile P 2 ligands in the dimers 1 and 2 could be substituted for the tetrahedral complexes B–E , which would direct the reactions towards selective pnictogen-rich coordination compounds that would possess two or more different types of pnictogen atoms. Herein we show that the reaction of the Ag( i ) dimer 1 with the tetrahedral clusters B–E or that of the Cu( i ) dimer 2 with B–C allow for the synthesis of the first and only heteroleptic complexes bearing two different types of organometallic tetrahedral molecules.…”