Exploring the Coordination Chemistry of N2 with Technetium PNP Pincer-Type Complexes

Abstract

Dinitrogen (N2) complexes of technetium (99Tc) are rare, and only two examples have been reported. To complement this important class of complexes also for 99Tc, two different pincer-type complexes of 99Tc were studied to assess their abilities for coordinating dinitrogen. The reactions of the 99TcIII complex [99TcCl3(PPh3)2(NCCH3)] with the pincer ligands PNPtBu and PyrPNPtBu respectively gave [99Tc(PNPtBu)Cl2] and [99Tc(PyrPNPtBu)Cl3], the first structurally characterized 99Tc complexes with mer-coordinated pincer ligands. Reductions with [Co(Cp*)2] under N2 gave the mononuclear bis-dinitrogen complex [99TcI(PNPtBu)(N2)2] and the dinuclear complex [99TcI(PyrPNPtBu)(N2)Cl]2(μ-N2) with both a bridging and a terminal N2 ligand. Spectroscopy and crystal structures confirm their identities. The complexes are stable under a dinitrogen atmosphere, and the N2 ligands are tightly bound. The results for the complexes with the PNPtBu pincer allow a comparison to its rhenium homologue, which has recently been shown to split the N2 ligand with the formation of a nitrido complex.