The gas‐phase ligand exchange of select magnesium and copper beta‐diketonate complexes

Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO oxide material are reported. Heterometallic compounds LiFeL (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac) (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac) (1) and LiFe(ptac) (2) that consist of discrete heterocyclic tetranuclear molecules LiFeL. The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L] peaks (M = LiFeL). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac) (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. H andLi NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure α-modification of layered oxide LiFeO, the prospective cathode material for lithium ion batteries.

show abstract

Heterometallic molecular precursors for a lithium–iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition

Han

Wei

Barry

et al. 2017

Dalton Trans.

View full text Add to dashboard Cite

show abstract

Three to tango requires a site-specific substitution: heterotrimetallic molecular precursors for high-voltage rechargeable batteries

et al. 2019

View full text Add to dashboard Cite

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

The gas‐phase ligand exchange of select magnesium and copper beta‐diketonate complexes

Abstract: Several gas-phase ligand exchange reactions were observed leading to the formation of both mixed and complete ligand exchange products. Copyright © 2016 John Wiley & Sons, Ltd.

Cited by 2 publications

References 18 publications

Heterometallic molecular precursors for a lithium–iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition

Heterometallic molecular precursors for a lithium–iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition

Three to tango requires a site-specific substitution: heterotrimetallic molecular precursors for high-voltage rechargeable batteries

Contact Info

Product

Resources

About