While dinitrogen is ubiquitous in nature the diphosphorus and diarsenic are transient species at ambient conditions due to weak multiple bonding for the heavier homologues. Several reports feature reduced {P2}n– and {As2}n- units stabilized by transition metal ions. The 2-pnictaethynolate anions [Na(dioxane)x][PnCO] (Pn = P, As) have proven to be excellent Pn sources for this purpose. Herein, we report the first terminal heavy pnictide complexes beyond group 6. Reaction of the octahedral Re(III) complex (PNP)ReI(PyrPz) (PNP = N{CH2CH2PtBu2}2, PyrPz = C8H6N3) with [Na(dioxane)x][PnCO] leads to the clean formation of the Re(V) pnictides (PNP)Re(Pn)(PyrPz). One electron oxidation results in Pn–Pn coupling to give (PNP)Re(Pn2-PyrPz) in 30-40 % yield. Bond analysis indicates pyrazole to Pn2 and Pn2 to Re donor-acceptor interactions, respectively, and the most appropriate description as neutral diphosphorus and diarsenic units with Pn=Pn double bonds.

Donor-acceptor stabilized P2 and As2 complexes from oxidative coupling of terminal rhenium pnictides

2019 Spring National Meeting

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