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

The reactions of tetrahedral molybdenum complexes bearing unsubstituted heterodiatomic Group 15 elements, [Cp 2 Mo 2 (CO) 4 (μ,η 2 :η 2 ‐PE)] (Cp=C 5 H 5 ; E=As ( 1 ), Sb ( 2 )), with Cu I halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo 2 PE units and the Cu I halide, the oligomers [⟨{Cp 2 Mo 2 (CO) 4 }{μ 4 ,η 2 :η 2 :η 2 :η 1 ‐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 [{Cp 2 Mo 2 (CO) 4 }{μ 4 ,η 2 :η 2 :η 1 :η 1 ‐PAs}{Cu(μ‐I)}] n ( 5 ) and [{Cp 2 Mo 2 (CO) 4 }{μ 4 ,η 2 :η 2 :η 2 :η 1 ‐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 Mo 2 PE 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 Cu I centers via the P lone pair and the P−E σ‐bond, revealing an unprecedented coordination mode.