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, [Cp2 Mo2 (CO)4 (µ,η2η2 -PE)] (Cp=C5 H5 ; E=As (1), Sb (2)), with CuI halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo2 PE units and the CuI halide, the oligomers [⟨{Cp2 Mo2 (CO)4 }{µ4 ,η2η2η2η1 -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 [{Cp2 Mo2 (CO)4 }{µ4 ,η2η2η1η1 -PAs}{Cu(µ-I)}]n (5) and [{Cp2 Mo2 (CO)4 }{µ4 ,η2η2η2η1 -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 Mo2 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 CuI centers via the P lone pair and the P-E σ-bond, revealing an unprecedented coordination mode.