Role of donor and secondary interactions in the structures and thermal properties of alkaline-earth and rare-earth metal pyrazolates

Julia Hitzbleck, Anna Y. O'Brien, Glen B. Deacon, Karin Ruhlandt

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The addition of neutral coligands to reduce the aggregation and improve the volatility of potential heavy alkaline-earth metal chemical vapor deposition (CVD) precursors has typically resulted in liberation of the coligand upon heating. A new series of dinuclear alkaline-earth and rare-earth metal pyrazolates, bis[bis(3,5-di-tert-butylpyrazolato)-(tetrahydrofuran)calcium] (1), bis[bis(3,5-di-tert-butylpyrazolato)(tetrahydrofuran)strontium] (2), and bis[bis(3,5-di-tert-butylpyrazolato)bis(tetrahydrofuran)barium] (3), have been obtained from our previous donor-free oligonuclear complexes [{M(3,5-tBu 2pz)2}n] (5, M = Ca, n = 3; 6, M = Sr, n = 4; 7, M = Ba, n = 6) by treatment with tetrahydrofuran (THF). Compounds 1-3, as well as the europium analogue bis[bis(3,5-di-tert-butylpyrazolato)- (tetrahydrofuran)europium(II)] (4), can also be prepared by direct reaction of the metals and pyrazole in THF and anhydrous liquid ammonia. Recrystallization from hexane led to single crystals of 2-4, while the powder diffraction pattern of 1 revealed it to be isostructural with the previously published bis[bis(3,5-di-tert-butylpyrazolato)-(tetrahydrofuran)ytterbium(II)] (8), providing important insight into differences and similarities between the two groups of metals. Detailed structural analysis of the compounds reveals secondary interactions including π-bonding and agostic interactions, which are considered essential in stabilizing the metal complexes. The direct comparison of structural features and thermal properties (as evaluated by thermogravimetric analysis and sublimation studies) of the donor-free oligonuclear and the donor-containing dinuclear species offers a better understanding of the role of donors and secondary interactions.

Original languageEnglish (US)
Pages (from-to)10329-10337
Number of pages9
JournalInorganic Chemistry
Volume45
Issue number25
DOIs
StatePublished - Dec 11 2006

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Rare Earth Metals
tetrahydrofuran
rare earth elements
Thermodynamic properties
thermodynamic properties
Earth (planet)
metals
Europium
interactions
europium
Ytterbium
Metals
Alkaline Earth Metals
liquid ammonia
Strontium
alkaline earth metals
volatility
Sublimation
Coordination Complexes
Hexanes

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Role of donor and secondary interactions in the structures and thermal properties of alkaline-earth and rare-earth metal pyrazolates. / Hitzbleck, Julia; O'Brien, Anna Y.; Deacon, Glen B.; Ruhlandt, Karin.

In: Inorganic Chemistry, Vol. 45, No. 25, 11.12.2006, p. 10329-10337.

Research output: Contribution to journalArticle

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