Toward a General Strategy for the Synthesis of Heterobimetallic Coordination Complexes for Use as Precursors to Metal Oxide Materials

Synthesis, Characterization, and Thermal Decomposition of Bi 2(Hsal)6·M(Acac)3 (M = Al, Co, V, Fe, Cr)

John H. Thurston, Daniel Trahan, Teyeb Ould-Ely, Kenton H. Whitmire

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

Bismuth(III) salicylate, [Bi(Hsal)3]n, reacts readily with the trivalent metal β-diketonate compounds M(acac) 3 (acac = acetylacetonate; M = Al, V, Cr, Fe, Co) to produce trinuclear coordination complexes of the general formula Bi 2(Hsal)6·M(acac)3 (M = Al, V, Cr, Fe, Co) in 60-90% yields. Spectroscopic and single crystal X-ray diffraction experiments indicate that these complexes possess an unusual asymmetric nested structure in both solution and solid state. Upon standing in dichloromethane solution, Bi2(Hsal)6·Co(acac)3 eliminates Bi(Hsal)3 to give the 1:1 adduct Bi(Hsal) 3·Co(acac)3. The 2:1 heterobimetallic molecular compounds undergo facile thermal decomposition on heating in air to 475 °C to produce heterometallic oxide materials, which upon annealing for 2 h at 700 °C form crystalline oxide materials. The synthetic approach detailed here represents a unique, general approach to the formation of heterobimetallic bismuth-based coordination complexes via the coordination of M(acac) 3 complexes to bismuth(III) salicylate.

Original languageEnglish
Pages (from-to)3299-3305
Number of pages7
JournalInorganic Chemistry
Volume43
Issue number10
DOIs
Publication statusPublished - May 17 2004
Externally publishedYes

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Bismuth
Coordination Complexes
Oxides
bismuth
thermal decomposition
metal oxides
salicylates
Pyrolysis
Salicylates
Metals
decomposition
synthesis
oxides
metal compounds
Methylene Chloride
adducts
Single crystals
Annealing
Crystalline materials
solid state

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Toward a General Strategy for the Synthesis of Heterobimetallic Coordination Complexes for Use as Precursors to Metal Oxide Materials : Synthesis, Characterization, and Thermal Decomposition of Bi 2(Hsal)6·M(Acac)3 (M = Al, Co, V, Fe, Cr). / Thurston, John H.; Trahan, Daniel; Ould-Ely, Teyeb; Whitmire, Kenton H.

In: Inorganic Chemistry, Vol. 43, No. 10, 17.05.2004, p. 3299-3305.

Research output: Contribution to journalArticle

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abstract = "Bismuth(III) salicylate, [Bi(Hsal)3]n, reacts readily with the trivalent metal β-diketonate compounds M(acac) 3 (acac = acetylacetonate; M = Al, V, Cr, Fe, Co) to produce trinuclear coordination complexes of the general formula Bi 2(Hsal)6·M(acac)3 (M = Al, V, Cr, Fe, Co) in 60-90{\%} yields. Spectroscopic and single crystal X-ray diffraction experiments indicate that these complexes possess an unusual asymmetric nested structure in both solution and solid state. Upon standing in dichloromethane solution, Bi2(Hsal)6·Co(acac)3 eliminates Bi(Hsal)3 to give the 1:1 adduct Bi(Hsal) 3·Co(acac)3. The 2:1 heterobimetallic molecular compounds undergo facile thermal decomposition on heating in air to 475 °C to produce heterometallic oxide materials, which upon annealing for 2 h at 700 °C form crystalline oxide materials. The synthetic approach detailed here represents a unique, general approach to the formation of heterobimetallic bismuth-based coordination complexes via the coordination of M(acac) 3 complexes to bismuth(III) salicylate.",
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AB - Bismuth(III) salicylate, [Bi(Hsal)3]n, reacts readily with the trivalent metal β-diketonate compounds M(acac) 3 (acac = acetylacetonate; M = Al, V, Cr, Fe, Co) to produce trinuclear coordination complexes of the general formula Bi 2(Hsal)6·M(acac)3 (M = Al, V, Cr, Fe, Co) in 60-90% yields. Spectroscopic and single crystal X-ray diffraction experiments indicate that these complexes possess an unusual asymmetric nested structure in both solution and solid state. Upon standing in dichloromethane solution, Bi2(Hsal)6·Co(acac)3 eliminates Bi(Hsal)3 to give the 1:1 adduct Bi(Hsal) 3·Co(acac)3. The 2:1 heterobimetallic molecular compounds undergo facile thermal decomposition on heating in air to 475 °C to produce heterometallic oxide materials, which upon annealing for 2 h at 700 °C form crystalline oxide materials. The synthetic approach detailed here represents a unique, general approach to the formation of heterobimetallic bismuth-based coordination complexes via the coordination of M(acac) 3 complexes to bismuth(III) salicylate.

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