Abstract
The preparation and spectroscopic identification of the complexes NNBe(η2‐N2) and (NN)2Be(η2‐N2) and the energetically higher lying isomers Be(NN)2 and Be(NN)3 are reported. NNBe(η2‐N2) and (NN)2Be(η2‐N2) are the first examples of covalently side‐on bonded N2 adducts of a main‐group element. The analysis of the electronic structure using modern methods of quantum chemistry suggests that NNBe(η2‐N2) and (NN)2Be(η2‐N2) should be classified as π complexes rather than metalladiazirines.
Highlights
Dinitrogen activation and its chemical transformations are one of the most challenging subjects in chemistry
The beryllium dinitrogen complexes were prepared by the reactions of pulsed laser evaporated beryllium atoms and dinitrogen in solid neon at 4 K
We report the preparation and spectroscopic identification of the complexes NNBe(h2-N2) (B) and (NN)2Be(h2-N2) (C) and the energetically higher lying isomers Be(NN)2 (A) and Be(NN)3 (D)
Summary
The p-bonding orbital of N2 (HOMO-1) acts as the donor orbital (Figure 1) As both s donation and p back-donation weaken the NÀN bond, the side-on mode results in a more activated N2 ligand than the end-on coordination. Very few weakly coordinated dinitrogen complexes of main-group elements have been observed in low-temperature noble-gas matrices or in the gas phase.[6,11,12,13,14,15,16,17,18,19,20] The main-group complexes are predominantly end-on-bound, with the exception of the LiN2 complex, for which a side-bound structure with almost purely ionic bonding has been proposed.[20] Recent studies show that reactive borylenes can bind N2 to form stable dinitrogen adducts and the reductive coupling of two hypovalent-boronbound N2 units mimics transition metals, which can be further protonated to derivatives,[21,22] demonstrating the feasibility of nitrogen fixation and reduction by nonmetal main-group species.[23] Here we report a joint matrix-isolation infrared spectroscopic and theoretical study on beryllium dinitrogen complexes involving a highly activated side-on bonded dinitrogen ligand. The structure, bonding, and reactivity of simple beryllium compounds serve as excellent model systems in achieving a thorough understanding of beryllium chemistry
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