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Updated: May 23, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Dinitrogen Activation with Low-Valent Strontium
Michael Morasch1, Timothy Vilpas1, Neha Patel1
1Inorganic and Organometallic Chemistry, Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058, Erlangen, Germany.
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 N2 2- 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-NDIPeP. A similar Ca product was also isolated (6-Ca). Crystal structures reveal a N2 2- 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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