RESUMO
The utilization of monomeric, lower phosphorous oxides and oxoanions, such as metaphosphite (PO2 - ), which is the heavier homologue of the common nitrite anion but previously only observed in the gas phase and by matrix isolation, requires new synthetic strategies. Herein, a series of rhenium(I-III) complexes with PO2 - as ligand is reported. Synthetic access was enabled by selective oxygenation of a terminal phosphide complex. Spectroscopic and computational examination revealed slightly stronger σ-donor and comparable π-acceptor properties of PO2 - compared to homologous NO2 - , which is one of the archetypal ligands in coordination chemistry.
RESUMO
The splitting of N2 into well-defined terminal nitride complexes is a key reaction for nitrogen fixation at ambient conditions. In continuation of our previous work on rhenium pincer mediated N2 splitting, nitrogen activation and cleavage upon (electro)chemical reduction of [ReCl2(L2)] {L2 = N(CHCHPtBu2)2 -} is reported. The electrochemical characterization of [ReCl2(L2)] and comparison with our previously reported platform [ReCl2(L1)] {L1 = N(CH2CH2PtBu2)2 -} provides mechanistic insight to rationalize the dependence of nitride yield on the reductant. Furthermore, the reactivity of N2 derived nitride complex [Re(N)Cl(L2)] with electrophiles is presented.
