An Experimental and Computational Investigation Rules Out Direct Nucleophilic Addition on the N Ligand in Manganese Dinitrogen Complex [Cp(CO) Mn(N )].

We have re-examined the reactivity of the manganese dinitrogen complex [Cp(CO) Mn(N )] (1, Cp=η -cyclopentadienyl, C H ) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N )MnCOPh]Li (3) that is stable only below -40 °C.

Dinitrogen-derived (diarylboryl)diazenido complexes with differing coordination to the thallium cation.

To prepare N-derived cationic boryldiazenido-tungsten complexes as models of semimetallic metal-borinium frustrated Lewis pairs activating N, we have attempted halide abstraction from -(diarylboryl)diazenido-halo-tungsten complexes. Reactions with Tl led to adducts in which coordination of the cation differs depending on the boryldiazenide substituents and the ancillary ligand. Chloride scavenging was not observed.