Panoply of P: An Array of Rhenium-Phosphorus Complexes Generated from a Transition Metal Anion.

We expand upon the synthetic utility of anionic rhenium complex Na[(BDI)ReCp] (, BDI = -bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) to generate several rhenium-phosphorus complexes. Complex reacts in a metathetical manner with chlorophosphines PhPCl, NHP-Cl, and OHP-Cl to generate XL-type phosphido complexes , , and , respectively (NHP-Cl = 2-chloro-1,3-dimethyl-1,3,2-diazaphospholidine; OHP-Cl = 2-chloro-1,3,2-dioxaphospholane). Crystallographic and computational investigations of phosphido triad , , and reveal that increasing the electronegativity of the phosphorus substituent (C < < O) results in a shortening and strengthening of the rhenium-phosphorus bond. Complex reacts with iminophosphane MesNPCl (Mes = 2,4,6-tri-butylphenyl) to generate linear iminophosphanyl complex . In the presence of a suitable halide abstraction reagent, reacts with the dichlorophosphine PrNPCl to afford cationic phosphinidene complex . Complex may be reduced by one electron to form , a rare example of a stable, paramagnetic phosphinidene complex. Spectroscopic and structural investigations, as well as computational analyses, are employed to elucidate the influence of the phosphorus substituent on the nature of the rhenium-phosphorus bond in through . Furthermore, we examine several common analogies employed to understand metal phosphido, phosphinidene, and iminophosphanyl complexes.