Non-photochemical synthesis of Re(diimine)(CO)2(L)Cl (L = phosphine or phosphite) compounds

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The synthesis and characterization of a series of compounds of the type Re(diimine)(CO)2(L)Cl (where L=P(OEt)3, PMe3) is reported. The non-photochemical ligand substitution (non-PLS) utilizes the trans-labilizing effect of phosphorus ligands to facilitate carbonyl replacement. The non-PLS pathway leads to good yields (>60%) of single isomer products, comparing favorably to the lower yield, mixed isomer products of analogous PLS pathways. The substitution of a carbonyl group by a phosphine/phosphite ligands shifts absorption further into the visible region without diminishing molar absorptivity. The synthesis presented provides a general facile ligand substitution pathway for related light-sensitive neutral rhenium/manganese carbonyl halide compounds.