Highly volatile alkaline earth metal fluoroalkoxides

William D. Buchanan, Marites A. Guino-O, Karin Ruhlandt

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The synthetic strategies, structural comparison, and thermal gravimetric analyses for a novel family of alkaline earth metal perfluoro-tert-butoxides (PFTB) are presented. The isolated complexes follow the general formula, [Ae(PFTB)2(d)x]; (1a, Ae = Mg, d = THF, x = 2; 1b, Ae = Ca, d = THF, x = 4; 1c, Ae = Sr, d = THF, x = 4; 1d, Ae = Ba, d = THF, x = 4; 2a, Ae = Mg, d = DME, x = 1; 2b, Ae = Ca, d = DME, x = 2; 2c, Ae = Sr, d = DME, x = 2; 2d, Ae = Ba, d = DME, x = 3; 3a, Ae = Mg, d = diglyme, x = 1; 3b, Ae = Ca, d = diglyme, x = 2; 3c, Ae = Sr, d = diglyme, x = 2; 3d, Ae = Ba, d = diglyme, x = 2; THF = tetrahydrofuran, DME = 1,2-dimethoxyethane) where the crystallographically characterized compounds display either a cis or trans conformations in octahedral or pseudo-octahedral environments. Alkane elimination (Mg), direct metalation via ammonia activation (Ca, Sr, Ba), and transamination (Ca, Sr, Ba) methods yielded the target compounds in moderate to good yields. Structural studies of select compounds showed all compounds to be monomeric with varying degrees of co-ligand coordination, possibly explaining some of the observed physical properties. Thermal gravimetric analyses of the compounds shows sublimation at low temperatures, associated with minimal residue, making this family of fluoroalkoxides promising candidates for metal organic chemical vapor deposition (MOCVD).

Original languageEnglish (US)
Pages (from-to)7144-7155
Number of pages12
JournalInorganic Chemistry
Volume49
Issue number15
DOIs
StatePublished - Aug 2 2010

Fingerprint

Alkaline Earth Metals
alkaline earth metals
tetrahydrofuran
sublimation
alkanes
metalorganic chemical vapor deposition
ammonia
elimination
physical properties
activation
ligands
Organic Chemicals
Alkanes
Sublimation
Ammonia
Conformations
Chemical vapor deposition
Physical properties
Metals
Chemical activation

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Highly volatile alkaline earth metal fluoroalkoxides. / Buchanan, William D.; Guino-O, Marites A.; Ruhlandt, Karin.

In: Inorganic Chemistry, Vol. 49, No. 15, 02.08.2010, p. 7144-7155.

Research output: Contribution to journalArticle

Buchanan, William D. ; Guino-O, Marites A. ; Ruhlandt, Karin. / Highly volatile alkaline earth metal fluoroalkoxides. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 15. pp. 7144-7155.
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AB - The synthetic strategies, structural comparison, and thermal gravimetric analyses for a novel family of alkaline earth metal perfluoro-tert-butoxides (PFTB) are presented. The isolated complexes follow the general formula, [Ae(PFTB)2(d)x]; (1a, Ae = Mg, d = THF, x = 2; 1b, Ae = Ca, d = THF, x = 4; 1c, Ae = Sr, d = THF, x = 4; 1d, Ae = Ba, d = THF, x = 4; 2a, Ae = Mg, d = DME, x = 1; 2b, Ae = Ca, d = DME, x = 2; 2c, Ae = Sr, d = DME, x = 2; 2d, Ae = Ba, d = DME, x = 3; 3a, Ae = Mg, d = diglyme, x = 1; 3b, Ae = Ca, d = diglyme, x = 2; 3c, Ae = Sr, d = diglyme, x = 2; 3d, Ae = Ba, d = diglyme, x = 2; THF = tetrahydrofuran, DME = 1,2-dimethoxyethane) where the crystallographically characterized compounds display either a cis or trans conformations in octahedral or pseudo-octahedral environments. Alkane elimination (Mg), direct metalation via ammonia activation (Ca, Sr, Ba), and transamination (Ca, Sr, Ba) methods yielded the target compounds in moderate to good yields. Structural studies of select compounds showed all compounds to be monomeric with varying degrees of co-ligand coordination, possibly explaining some of the observed physical properties. Thermal gravimetric analyses of the compounds shows sublimation at low temperatures, associated with minimal residue, making this family of fluoroalkoxides promising candidates for metal organic chemical vapor deposition (MOCVD).

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