Nuclear magnetic resonance study of structural dynamics in μ-carbonyl-bis-μ-stannylene-diiron hexacarbonyl clusters

Gregory W. Grynkewich, Tobin J Marks

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Abstract

The compound [μ-(C6H5)(CH3)Sn]2Fe 2(CO)7 was synthesized to differentiate bridge deformation from iron-tin bond cleavage in R group interchange processes of stereochemically nonrigid [μ-R2Sn]2Fe2(CO)7 complexes. It is found from proton NMR studies that both processes can occur, the former with ΔG = 11.8 ± 0.6 kcal/mol (298 K) and the latter with ΔG = 19.2 ± 0.9 kcal/mol (298 K). The bridge deformation in the related, more soluble molecule [(n-C4H9)2Sn]2Fe 2(CO)7 occurs with simultaneous, stereospecific interchange of bridge and terminal carbonyl ligands, as monitored by 13C NMR spectra. The complex [(C6H5)(CH3)SnFe(CO)4]2 exists in two isomeric forms which interconvert in solution with AG = 25.5 ± 0.7 kcal/mol (298 K). The iron-tin bond cleavages are proposed to yield R2Sn→Fe stannylene intermediates.

Original languageEnglish
Pages (from-to)1307-1314
Number of pages8
JournalInorganic Chemistry
Volume15
Issue number6
Publication statusPublished - 1976

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dynamic structural analysis
Structural dynamics
Carbon Monoxide
Nuclear magnetic resonance
nuclear magnetic resonance
Tin
cleavage
tin
Interchanges
iron
Iron
Protons
ligands
protons
Ligands
Molecules
molecules

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Nuclear magnetic resonance study of structural dynamics in μ-carbonyl-bis-μ-stannylene-diiron hexacarbonyl clusters. / Grynkewich, Gregory W.; Marks, Tobin J.

In: Inorganic Chemistry, Vol. 15, No. 6, 1976, p. 1307-1314.

Research output: Contribution to journalArticle

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abstract = "The compound [μ-(C6H5)(CH3)Sn]2Fe 2(CO)7 was synthesized to differentiate bridge deformation from iron-tin bond cleavage in R group interchange processes of stereochemically nonrigid [μ-R2Sn]2Fe2(CO)7 complexes. It is found from proton NMR studies that both processes can occur, the former with ΔG‡ = 11.8 ± 0.6 kcal/mol (298 K) and the latter with ΔG‡ = 19.2 ± 0.9 kcal/mol (298 K). The bridge deformation in the related, more soluble molecule [(n-C4H9)2Sn]2Fe 2(CO)7 occurs with simultaneous, stereospecific interchange of bridge and terminal carbonyl ligands, as monitored by 13C NMR spectra. The complex [(C6H5)(CH3)SnFe(CO)4]2 exists in two isomeric forms which interconvert in solution with AG‡ = 25.5 ± 0.7 kcal/mol (298 K). The iron-tin bond cleavages are proposed to yield R2Sn→Fe stannylene intermediates.",
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N2 - The compound [μ-(C6H5)(CH3)Sn]2Fe 2(CO)7 was synthesized to differentiate bridge deformation from iron-tin bond cleavage in R group interchange processes of stereochemically nonrigid [μ-R2Sn]2Fe2(CO)7 complexes. It is found from proton NMR studies that both processes can occur, the former with ΔG‡ = 11.8 ± 0.6 kcal/mol (298 K) and the latter with ΔG‡ = 19.2 ± 0.9 kcal/mol (298 K). The bridge deformation in the related, more soluble molecule [(n-C4H9)2Sn]2Fe 2(CO)7 occurs with simultaneous, stereospecific interchange of bridge and terminal carbonyl ligands, as monitored by 13C NMR spectra. The complex [(C6H5)(CH3)SnFe(CO)4]2 exists in two isomeric forms which interconvert in solution with AG‡ = 25.5 ± 0.7 kcal/mol (298 K). The iron-tin bond cleavages are proposed to yield R2Sn→Fe stannylene intermediates.

AB - The compound [μ-(C6H5)(CH3)Sn]2Fe 2(CO)7 was synthesized to differentiate bridge deformation from iron-tin bond cleavage in R group interchange processes of stereochemically nonrigid [μ-R2Sn]2Fe2(CO)7 complexes. It is found from proton NMR studies that both processes can occur, the former with ΔG‡ = 11.8 ± 0.6 kcal/mol (298 K) and the latter with ΔG‡ = 19.2 ± 0.9 kcal/mol (298 K). The bridge deformation in the related, more soluble molecule [(n-C4H9)2Sn]2Fe 2(CO)7 occurs with simultaneous, stereospecific interchange of bridge and terminal carbonyl ligands, as monitored by 13C NMR spectra. The complex [(C6H5)(CH3)SnFe(CO)4]2 exists in two isomeric forms which interconvert in solution with AG‡ = 25.5 ± 0.7 kcal/mol (298 K). The iron-tin bond cleavages are proposed to yield R2Sn→Fe stannylene intermediates.

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