Two in one: a facile modular approach for the assembly of pnictogen-rich heteroleptic organometallic complexes

Abstract

The reactions between soluble 1D polymer [Ag{(η²:η¹-A)}₂]_n[TEF]_n, obtained from five-fold symmetric building blocks [Cp*Fe(η⁵-P₅)] (A, Cp* = η⁵-C₅Me₅) and a weakly coordinating salt of Ag(I), and a series of ditopic–tetrahedral organometallic building blocks, [{CpMo(CO)₂}₂(η²-E₂)] (E = P, As) or [{CpMo(CO)₂}₂(η²-PE)] (E = As, Sb), have been investigated. It is shown that, depending on the choice of the ditopic–tetrahedral complexes, a rational design of unprecedented heteroleptic 1D polymer or discrete molecular systems containing two different pnictogenyl building blocks is possible. Weak π–π interactions, adaptive coordination behavior of the Ag(I), argentophilic interactions and the fine-tuned electronic properties of the ditopic–tetrahedral complexes directed the product formation. The modular synthetic approach paves the way for hybrid systems containing heteroleptic pnictogen-rich supramolecular assemblies.