The Potential of Molybdenum Complexes Bearing Unsubstituted Heterodiatomic Group 15 Elements as Linkers in Supramolecular Chemistry

Abstract

The reactions of tetrahedral molybdenum complexes bearing unsubstituted heterodiatomic Group 15 elements, [Cp2Mo2(CO)4(μ,η2:η2-PE)] (Cp=C5H5; E=As (1), Sb (2)), with CuI halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo2PE units and the CuI halide, the oligomers [⟨{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1-PE}⟩4⟨{CuX}{Cu(μ-X)}⟩2] (E=As (X=Cl (3), Br (4)); E=Sb (X=Cl (6), Br (7))) or the 1D coordination polymers [{Cp2Mo2(CO)4}{μ4,η2:η2:η1:η1-PAs}{Cu(μ-I)}]n (5) and [{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1-PSb}2{Cu(μ-X)}3]n (X=I (8), Br (9)) are accessible. These solid-state aggregates are the first and only examples featuring the organometallic heterodiatomic Mo2PE complexes 1 and 2 as linking moieties. DFT calculations demonstrate that complexes 1 and 2 present a unique class of mixed-donor ligands coordinating to CuI centers via the P lone pair and the P−E σ-bond, revealing an unprecedented coordination mode.