Dinitrogen Activation with Low-Valent Strontium

Morasch M, Vilpas T, Patel N, Maurer J, Thum S, Schmidt M, Langer J, Harder S (2025)

Publication Type: Journal article

Publication year: 2025

Journal

DOI: 10.1002/anie.202506989

Abstract

DFT calculations on β-diketiminate (BDI) complexes with the full series of alkaline-earth (Ae) metals show that (BDI)AeAe(BDI) complexes of the heavier Ae metals (Ca, Sr, Ba) have long weak Ae─Ae bonds that are prone to homolytic bond cleavage. However, isolation of (BDI)Sr(μ-N2)Sr(BDI) with a side-on bridging N2²⁻ dianion should thermodynamically be feasible. Attempts to stabilize such a complex with the super bulky BDI* ligand failed (BDI* = HC[(Me)C = N-DIPeP]2, DIPeP = 2,6-Et2CH-phenyl). First, N2 fixation with a Sr complex was enabled by a heterobimetallic approach. Reduction of (^DIPePNN)Sr with potassium gave (^DIPePNN)2Sr2K2(N2) (6-Sr); ^DIPePNN = ^DIPePN-Si(Me)2CH2CH2Si(Me)2-N^DIPeP. A similar Ca product was also isolated (6-Ca). Crystal structures reveal a N2²⁻ anion with side-on bonding to Ae²⁺ and end-on coordination to K⁺. DFT calculations and Atoms-In-Molecules analyses show mainly ionic bonding. Both 6-Ae complexes are synthons for hitherto unknown (BDI*)AeAe(BDI*) (Ae = Ca, Sr) and react by releasing N2 and two electrons. Although surprisingly stable in benzene, the reduction of I2 and H2 is facile. Fast reaction with Teflon led to formation of crystalline [(^DIPePNN)SrKF]2 (7), which is labile and decomposed to KF and (^DIPePNN)Sr. Latter reactivity underscores potential use of 6-Ae complexes as very strong, hydrocarbon-soluble reducing agents.

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How to cite

APA:

Morasch, M., Vilpas, T., Patel, N., Maurer, J., Thum, S., Schmidt, M.,... Harder, S. (2025). Dinitrogen Activation with Low-Valent Strontium. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.202506989

MLA:

Morasch, Michael, et al. "Dinitrogen Activation with Low-Valent Strontium." Angewandte Chemie International Edition (2025).

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